A metal-mediated dimerization of the ligand bis(N,N-diethyl­amino)­carbeniumdi­thio­carboxyl­ate

The title compound, methylene bis[bis(N,N-diethyl­amino)­carbeniumdi­thio­carboxyl­ate] penta­chloro­oxo­rhenium, (C₂₁H₄₂N₄S₄)[ReCl₅O], is the result of an unusual dimerization of the ligand bis(N,N-diethyl­amino)­carbeniumdi­thio­carboxyl­ate [(Et₂N)₂C₂S₂] upon reaction with [ReOCl₃(PPh₃)₂] in chloro­form under reflux conditions. The compound was obtained as a dicationic moiety, with the molecular [ReOCl₅]^2- anion providing the charge compensation. The planes of the carbenium and thio­carboxyl­ate moieties are nearly perpendicular to one another and the backbone C-C bond length in the N₂CCS₂ group is the same as a normal C-C single-bond length.

S1. Comment

The ligand bis(N,N-diethylamino)carbeniumdithiocarboxylate, [(Et₂N)₂C₂S₂], (I), was first synthesized by Nakayama et al. (1992, 1995, 2000) and was proposed to possess an interesting inner-salt structure, in which the positive and negative charges are delocalized on the NCN and SCS moieties, although the structure can be drawn as canonical contributions between an inner-salt form and a neutral form.

In previous X-ray structural studies of the rheniumtricarbonyl complexes with ligand (I) (Banerjee et al., 2002), we have observed that the ligand can act as a neutral bridging ligand, as well as a bidentate chelating ligand, maintaining its characteristic inner-salt structural features. As part of our ongoing interest in exploring the versatility of the ligand's binding mode, we have studied the reactions of the ligand with different oxorhenium(V) starting materials. We report here the structural characterization of a new compound, (II), obtained upon refluxing a chloroform solution the common oxorhenium(V) starting material [ReOCl₃(PPh₃)₂] with ligand (I).

A perspective view of (II) is shown in Fig. 1, and selected bond lengths and angles for (II) are given in Table 1. The structure of (II) can be described as a dimer of the [(Et₂N)₂C₂S₂] unit connected via a methylene group at the C21 position, maintaining essentially the same structural features of the [(Et₂N)₂C₂S₂] ligand. The S1—C21—S3 bridging angle is 113.64 (12) °, a significant deviation from the idealized tetrahedral angle, while the two C=S terminal bonds are oriented trans to one another, thus minimizing the steric interaction between the ligand halves. The Re—O bond length is 1.6796 (17) Å and lies within the range of normal values of Reτb O triple-bond values, [1.68 (3) Å; Banerjee et al., 2000, and references therein). The Re—Cl bond lengths lie in the range 2.3896 (6)–2.4550 (5) Å and are within the range of normal values (Gilli et al., 1982; Sivakumar et al., 1998; Banerjee et al., 2000) The Re–Cl3 bond is the longest bond, as it lies trans to the Reτb O triple bond. The metric parameters for the organic cation are significant, as they define the electronic structure of the ligand. The backbone C9—C10 and C11—12 bonds are longer (ca 0.02 Å) than that of the free ligand, (I) [1.47 (2) Å; Nakayama, 1995]. The C—N bond lengths are shorter and are close to the normal Cδb N double-bond length [1.316 (9) Å; Allen et al., 1987]. The N—C—N bond angles [125.4 (2) and 126.5 (2)°] are close to the value for the free ligand [122 (1)°]. The most significant features of (II) are the dihedral angles between the S/C/S and N/C/N planes, viz. 104.5 (2)° (S4/C11/S3 and N2/C12/N4) and 104.7 (2)° (S1/C10/S2 and N1/C9/N2), respectively, for the two halves of the ligand. These dihedral angles are significantly larger than that observed in the free ligand [98.0 (1)°; Nakayama, 1995]. There are different kinds of C—S bond lengths in the compound. The S2—C10 and S4—C11 bonds [1.615 (2) and 1.635 (2) Å, respectively] are close to the Cδb S double-bond value (Allen et al., 1987) and much shorter than that of the free ligand [1.67 (2)–1.68 (2) Å]. The S1—C10 [1.740 (2) Å] and S3—C11 [1.708 (2) Å] bonds display multiple-bond character. The S1—C21 and S3—C21 bond lengths are 1.800 (2) and 1.801 (2) Å, respectively, and are comparable to the normal C—S single-bond laength [1.79–1.82 (1) Å; Miller et al., 2000].

S2. Experimental

To solution of [ReOCl₃PPh₃)₂] (0.1 g, 0.12 mmol) in chloroform (15 ml) was added the ligand [(Et₂N)₂C₂S₂] (0.083 mg, 0. 36 mmol) (Nakayama et al., 1992) and the solution was refluxed for 5 h. The resulting dark-brown reaction mixture was subjected to chromatographic separation (MeOH/CH₂Cl₂ 2:98) using a silica-gel column. The light-pink–orange fraction was collected and evaporated under vacuum to give an orange solid. Yield: 32 mg, 30%. Analysis found: C 29.95, H 5.24, N 6.58%; C₂₁H₄₂C_l5N₄OReS₄ requires: C 29.35, H 5.04, N 6.52%. Crystals of (II) suitable for single-crystal X-ray diffraction were grown by slow diffusion of a solution of (II) in CH₂Cl₂ into hexane solution at room temperature.

S3. Refinement

All H atoms were located in difference Fourier maps and then allowed for as riding atoms, with U_iso(H) values of 1.2U_eq(parent atom). A residual peak of electron density was located in the vicinity of the Re atom. However, the absorption correction could not be adjusted to further minimize this residual. Such residuals are not uncommon in structures containing atoms with large absorption coefficients.

Computing details

Data collection: SMART (Bruker, 1997); cell refinement: SMART; data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A view of (II), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms have been omitted for clarity.

(II)

Crystal data

(C21H42N4S4)[ReCl5O]	F(000) = 1712
Mr = 858.28	Dx = 1.694 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 11209 reflections
a = 13.1381 (5) Å	θ = 1.8–31.5°
b = 16.3486 (7) Å	µ = 4.28 mm^−1
c = 15.7094 (6) Å	T = 90 K
β = 94.003 (1)°	Block, orange
V = 3366.0 (2) Å^3	0.23 × 0.16 × 0.10 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-dectector diffractometer	11209 independent reflections
Radiation source: fine-focus sealed tube	10065 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
Detector resolution: 512 pixels mm^-1	θmax = 31.5°, θmin = 1.8°
φ and ω scans	h = −19→19
Absorption correction: multi-scan (SADABS; Sheldrick, 1997)	k = −24→23
Tmin = 0.440, Tmax = 0.674	l = −23→23
43155 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.064	H-atom parameters constrained
S = 1.07	w = 1/[σ^2(Fo^2) + (0.031P)^2 + 2.8947P] where P = (Fo^2 + 2Fc^2)/3
11209 reflections	(Δ/σ)max = 0.003
333 parameters	Δρmax = 1.83 e Å^−3
0 restraints	Δρmin = −0.47 e Å^−3

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. Highest peak 1.82 at 0.9835 0.2405 0.0204 [0.74 A from Re1] Deepest hole -0.47 at 0.0643 0.1918 0.0451 [1.20 A from Cl2]

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

	x	y	z	Uiso*/Ueq
Re1	0.527008 (6)	0.696602 (5)	0.487325 (5)	0.01556 (3)
Cl1	0.56523 (5)	0.68897 (3)	0.34104 (3)	0.02233 (11)
Cl2	0.35210 (4)	0.72002 (3)	0.43906 (4)	0.02062 (10)
Cl3	0.55376 (4)	0.84493 (3)	0.47914 (3)	0.01948 (10)
Cl4	0.49064 (4)	0.72411 (3)	0.63348 (3)	0.01993 (10)
Cl5	0.70669 (4)	0.69182 (3)	0.53003 (4)	0.02193 (10)
S1	0.23796 (4)	−0.07465 (4)	0.64456 (3)	0.01979 (10)
S2	0.44490 (4)	0.00497 (4)	0.67031 (4)	0.02377 (11)
S3	0.33135 (4)	−0.05591 (3)	0.47577 (3)	0.01641 (9)
S4	0.10904 (5)	−0.10405 (5)	0.45207 (4)	0.03147 (14)
O1	0.51257 (14)	0.59535 (10)	0.49998 (11)	0.0234 (3)
N1	0.26601 (15)	0.11146 (12)	0.76211 (12)	0.0179 (3)
N2	0.28109 (15)	−0.01116 (12)	0.84195 (12)	0.0193 (4)
N3	0.20680 (16)	−0.05274 (12)	0.27073 (12)	0.0209 (4)
N4	0.20663 (14)	0.07070 (12)	0.34890 (12)	0.0182 (3)
C1	0.3892 (2)	0.18456 (18)	0.85998 (18)	0.0308 (6)
H1A	0.4192	0.1326	0.8803	0.046*
H1B	0.3959	0.2251	0.9059	0.046*
H1C	0.4249	0.2041	0.8112	0.046*
C2	0.27751 (18)	0.17193 (14)	0.83301 (15)	0.0209 (4)
H2A	0.2413	0.1520	0.8822	0.025*
H2B	0.2465	0.2247	0.8141	0.025*
C3	0.24901 (18)	0.14949 (14)	0.67623 (14)	0.0208 (4)
H3A	0.2668	0.1097	0.6321	0.025*
H3B	0.2941	0.1977	0.6725	0.025*
C4	0.1394 (2)	0.1756 (2)	0.65947 (18)	0.0333 (6)
H4A	0.0953	0.1272	0.6567	0.050*
H4B	0.1315	0.2052	0.6051	0.050*
H4C	0.1201	0.2115	0.7057	0.050*
C5	0.2601 (3)	0.03196 (18)	0.99382 (16)	0.0342 (6)
H5A	0.2943	−0.0163	1.0194	0.051*
H5B	0.2086	0.0515	1.0312	0.051*
H5C	0.3105	0.0752	0.9866	0.051*
C6	0.2091 (2)	0.00954 (16)	0.90794 (16)	0.0257 (5)
H6A	0.1637	−0.0379	0.9153	0.031*
H6B	0.1659	0.0559	0.8870	0.031*
C7	0.4436 (2)	−0.07757 (19)	0.89654 (18)	0.0333 (6)
H7A	0.4825	−0.0425	0.8599	0.050*
H7B	0.4776	−0.1308	0.9035	0.050*
H7C	0.4401	−0.0517	0.9525	0.050*
C8	0.33634 (19)	−0.08960 (15)	0.85568 (15)	0.0230 (4)
H8A	0.3403	−0.1177	0.8002	0.028*
H8B	0.2976	−0.1252	0.8928	0.028*
C9	0.28891 (17)	0.03281 (14)	0.77096 (13)	0.0180 (4)
C10	0.32944 (17)	−0.01113 (13)	0.69539 (13)	0.0177 (4)
C11	0.21236 (17)	−0.05829 (14)	0.42455 (13)	0.0185 (4)
C12	0.20880 (16)	−0.01000 (14)	0.34226 (13)	0.0174 (4)
C13	0.17542 (18)	0.11199 (15)	0.42693 (15)	0.0219 (4)
H13A	0.2286	0.1517	0.4472	0.026*
H13B	0.1684	0.0710	0.4725	0.026*
C14	0.0748 (2)	0.1563 (2)	0.40878 (17)	0.0326 (6)
H14A	0.0810	0.1951	0.3619	0.049*
H14B	0.0572	0.1859	0.4600	0.049*
H14C	0.0211	0.1164	0.3927	0.049*
C15	0.23491 (19)	0.12923 (15)	0.28213 (16)	0.0248 (5)
H15A	0.2331	0.1855	0.3052	0.030*
H15B	0.1838	0.1259	0.2328	0.030*
C16	0.3402 (2)	0.11255 (17)	0.2518 (2)	0.0328 (6)
H16A	0.3915	0.1183	0.2998	0.049*
H16B	0.3546	0.1517	0.2070	0.049*
H16C	0.3425	0.0568	0.2290	0.049*
C17	0.2428 (2)	−0.13907 (15)	0.26885 (15)	0.0239 (5)
H17A	0.1940	−0.1719	0.2320	0.029*
H17B	0.2448	−0.1622	0.3272	0.029*
C18	0.3472 (2)	−0.14469 (18)	0.2355 (2)	0.0357 (6)
H18A	0.3455	−0.1208	0.1782	0.054*
H18B	0.3678	−0.2022	0.2330	0.054*
H18C	0.3962	−0.1147	0.2736	0.054*
C19	0.1568 (2)	−0.02289 (17)	0.18869 (15)	0.0289 (5)
H19A	0.1659	−0.0638	0.1434	0.035*
H19B	0.1897	0.0287	0.1721	0.035*
C20	0.0441 (2)	−0.00819 (17)	0.19656 (18)	0.0338 (6)
H20A	0.0113	−0.0595	0.2116	0.051*
H20B	0.0130	0.0119	0.1420	0.051*
H20C	0.0352	0.0326	0.2412	0.051*
C21	0.31190 (19)	−0.12135 (14)	0.56544 (13)	0.0198 (4)
H21A	0.2769	−0.1718	0.5445	0.024*
H21B	0.3792	−0.1373	0.5926	0.024*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Re1	0.02031 (4)	0.01289 (4)	0.01363 (4)	−0.00065 (3)	0.00217 (3)	0.00047 (3)
Cl1	0.0321 (3)	0.0199 (2)	0.0157 (2)	−0.0035 (2)	0.0062 (2)	−0.00073 (18)
Cl2	0.0214 (2)	0.0188 (2)	0.0212 (2)	−0.00087 (19)	−0.00135 (19)	−0.00199 (19)
Cl3	0.0221 (2)	0.0140 (2)	0.0225 (2)	−0.00073 (18)	0.00293 (19)	0.00165 (17)
Cl4	0.0257 (2)	0.0204 (2)	0.0140 (2)	0.00225 (19)	0.00389 (18)	0.00136 (18)
Cl5	0.0212 (2)	0.0203 (2)	0.0242 (3)	0.00323 (19)	0.0004 (2)	−0.00134 (19)
S1	0.0233 (3)	0.0202 (2)	0.0158 (2)	−0.0043 (2)	0.00117 (19)	−0.00278 (19)
S2	0.0196 (2)	0.0292 (3)	0.0227 (3)	−0.0026 (2)	0.0028 (2)	−0.0029 (2)
S3	0.0181 (2)	0.0166 (2)	0.0141 (2)	0.00019 (18)	−0.00176 (17)	0.00108 (18)
S4	0.0257 (3)	0.0434 (4)	0.0248 (3)	−0.0162 (3)	−0.0022 (2)	0.0066 (3)
O1	0.0343 (9)	0.0156 (7)	0.0206 (8)	−0.0016 (7)	0.0033 (7)	0.0011 (6)
N1	0.0230 (9)	0.0154 (8)	0.0153 (8)	−0.0033 (7)	0.0013 (7)	−0.0014 (6)
N2	0.0235 (9)	0.0184 (8)	0.0164 (8)	−0.0018 (7)	0.0040 (7)	−0.0010 (7)
N3	0.0283 (10)	0.0195 (9)	0.0143 (8)	0.0004 (8)	−0.0024 (7)	0.0006 (7)
N4	0.0199 (8)	0.0181 (8)	0.0163 (8)	0.0001 (7)	−0.0005 (7)	0.0015 (7)
C1	0.0289 (13)	0.0355 (14)	0.0275 (12)	−0.0117 (11)	−0.0007 (10)	−0.0043 (10)
C2	0.0256 (11)	0.0173 (10)	0.0200 (10)	−0.0025 (8)	0.0024 (8)	−0.0039 (8)
C3	0.0258 (11)	0.0186 (10)	0.0184 (9)	−0.0006 (8)	0.0041 (8)	0.0022 (8)
C4	0.0291 (13)	0.0455 (16)	0.0249 (12)	0.0037 (12)	−0.0013 (10)	0.0062 (11)
C5	0.0552 (18)	0.0287 (13)	0.0203 (11)	0.0052 (12)	0.0136 (11)	0.0019 (10)
C6	0.0295 (12)	0.0234 (11)	0.0259 (11)	−0.0019 (9)	0.0133 (10)	0.0020 (9)
C7	0.0298 (13)	0.0405 (15)	0.0295 (13)	0.0070 (12)	0.0011 (10)	−0.0002 (11)
C8	0.0300 (12)	0.0219 (11)	0.0169 (10)	0.0021 (9)	0.0012 (8)	0.0010 (8)
C9	0.0197 (9)	0.0192 (10)	0.0150 (9)	−0.0032 (8)	0.0008 (7)	−0.0019 (7)
C10	0.0225 (10)	0.0176 (9)	0.0127 (8)	−0.0001 (8)	−0.0001 (7)	−0.0003 (7)
C11	0.0211 (10)	0.0194 (10)	0.0146 (9)	−0.0030 (8)	−0.0022 (7)	0.0002 (7)
C12	0.0182 (9)	0.0189 (10)	0.0148 (9)	−0.0007 (8)	−0.0019 (7)	0.0023 (7)
C13	0.0243 (11)	0.0205 (10)	0.0208 (10)	0.0037 (9)	−0.0003 (8)	−0.0019 (8)
C14	0.0266 (12)	0.0476 (17)	0.0244 (12)	0.0140 (12)	0.0070 (10)	0.0082 (11)
C15	0.0270 (11)	0.0196 (11)	0.0289 (12)	0.0030 (9)	0.0093 (9)	0.0067 (9)
C16	0.0305 (13)	0.0245 (12)	0.0454 (16)	0.0017 (10)	0.0176 (12)	0.0027 (11)
C17	0.0327 (12)	0.0181 (10)	0.0203 (10)	−0.0024 (9)	−0.0034 (9)	−0.0049 (8)
C18	0.0271 (13)	0.0271 (13)	0.0520 (18)	−0.0026 (10)	−0.0031 (12)	−0.0123 (12)
C19	0.0442 (15)	0.0287 (12)	0.0128 (9)	−0.0016 (11)	−0.0048 (9)	0.0030 (9)
C20	0.0428 (15)	0.0283 (13)	0.0276 (12)	0.0067 (12)	−0.0162 (11)	−0.0020 (10)
C21	0.0308 (11)	0.0157 (9)	0.0127 (9)	0.0024 (8)	−0.0004 (8)	0.0009 (7)

Geometric parameters (Å, º)

Re1—O1	1.6796 (17)	C5—H5B	0.9800
Re1—Cl1	2.3896 (6)	C5—H5C	0.9800
Re1—Cl2	2.3998 (6)	C6—H6A	0.9900
Re1—Cl5	2.4099 (6)	C6—H6B	0.9900
Re1—Cl4	2.4199 (5)	C7—C8	1.521 (4)
Re1—Cl3	2.4550 (5)	C7—H7A	0.9800
S1—C10	1.740 (2)	C7—H7B	0.9800
S1—C21	1.800 (2)	C7—H7C	0.9800
S2—C10	1.615 (2)	C8—H8A	0.9900
S3—C11	1.708 (2)	C8—H8B	0.9900
S3—C21	1.801 (2)	C9—C10	1.516 (3)
S4—C11	1.634 (2)	C11—C12	1.513 (3)
N1—C9	1.326 (3)	C13—C14	1.517 (3)
N1—C3	1.488 (3)	C13—H13A	0.9900
N1—C2	1.489 (3)	C13—H13B	0.9900
N2—C9	1.337 (3)	C14—H14A	0.9800
N2—C8	1.482 (3)	C14—H14B	0.9800
N2—C6	1.490 (3)	C14—H14C	0.9800
N3—C12	1.322 (3)	C15—C16	1.519 (3)
N3—C19	1.487 (3)	C15—H15A	0.9900
N3—C17	1.489 (3)	C15—H15B	0.9900
N4—C12	1.324 (3)	C16—H16A	0.9800
N4—C13	1.482 (3)	C16—H16B	0.9800
N4—C15	1.486 (3)	C16—H16C	0.9800
C1—C2	1.513 (4)	C17—C18	1.505 (4)
C1—H1A	0.9800	C17—H17A	0.9900
C1—H1B	0.9800	C17—H17B	0.9900
C1—H1C	0.9800	C18—H18A	0.9800
C2—H2A	0.9900	C18—H18B	0.9800
C2—H2B	0.9900	C18—H18C	0.9800
C3—C4	1.508 (4)	C19—C20	1.513 (4)
C3—H3A	0.9900	C19—H19A	0.9900
C3—H3B	0.9900	C19—H19B	0.9900
C4—H4A	0.9800	C20—H20A	0.9800
C4—H4B	0.9800	C20—H20B	0.9800
C4—H4C	0.9800	C20—H20C	0.9800
C5—C6	1.509 (4)	C21—H21A	0.9900
C5—H5A	0.9800	C21—H21B	0.9900
O1—Re1—Cl1	95.48 (6)	N2—C8—H8A	109.1
O1—Re1—Cl2	94.65 (6)	C7—C8—H8A	109.1
Cl1—Re1—Cl2	88.01 (2)	N2—C8—H8B	109.1
O1—Re1—Cl5	92.96 (6)	C7—C8—H8B	109.1
Cl1—Re1—Cl5	89.91 (2)	H8A—C8—H8B	107.9
Cl2—Re1—Cl5	172.271 (19)	N1—C9—N2	125.4 (2)
O1—Re1—Cl4	92.26 (6)	N1—C9—C10	117.84 (19)
Cl1—Re1—Cl4	172.263 (19)	N2—C9—C10	116.77 (19)
Cl2—Re1—Cl4	91.260 (19)	C9—C10—S2	120.08 (16)
Cl5—Re1—Cl4	89.79 (2)	C9—C10—S1	111.91 (15)
O1—Re1—Cl3	175.95 (6)	S2—C10—S1	128.00 (13)
Cl1—Re1—Cl3	87.753 (18)	C12—C11—S4	119.22 (16)
Cl2—Re1—Cl3	87.898 (19)	C12—C11—S3	111.31 (16)
Cl5—Re1—Cl3	84.581 (18)	S4—C11—S3	129.47 (14)
Cl4—Re1—Cl3	84.523 (18)	N3—C12—N4	126.5 (2)
C10—S1—C21	100.44 (11)	N3—C12—C11	116.6 (2)
C11—S3—C21	100.36 (11)	N4—C12—C11	116.90 (19)
C9—N1—C3	121.26 (18)	N4—C13—C14	110.47 (19)
C9—N1—C2	123.72 (19)	N4—C13—H13A	109.6
C3—N1—C2	113.69 (18)	C14—C13—H13A	109.6
C9—N2—C8	121.42 (19)	N4—C13—H13B	109.6
C9—N2—C6	123.2 (2)	C14—C13—H13B	109.6
C8—N2—C6	115.06 (19)	H13A—C13—H13B	108.1
C12—N3—C19	123.0 (2)	C13—C14—H14A	109.5
C12—N3—C17	122.03 (19)	C13—C14—H14B	109.5
C19—N3—C17	114.53 (19)	H14A—C14—H14B	109.5
C12—N4—C13	121.85 (19)	C13—C14—H14C	109.5
C12—N4—C15	125.3 (2)	H14A—C14—H14C	109.5
C13—N4—C15	112.81 (19)	H14B—C14—H14C	109.5
C2—C1—H1A	109.5	N4—C15—C16	112.6 (2)
C2—C1—H1B	109.5	N4—C15—H15A	109.1
H1A—C1—H1B	109.5	C16—C15—H15A	109.1
C2—C1—H1C	109.5	N4—C15—H15B	109.1
H1A—C1—H1C	109.5	C16—C15—H15B	109.1
H1B—C1—H1C	109.5	H15A—C15—H15B	107.8
N1—C2—C1	110.2 (2)	C15—C16—H16A	109.5
N1—C2—H2A	109.6	C15—C16—H16B	109.5
C1—C2—H2A	109.6	H16A—C16—H16B	109.5
N1—C2—H2B	109.6	C15—C16—H16C	109.5
C1—C2—H2B	109.6	H16A—C16—H16C	109.5
H2A—C2—H2B	108.1	H16B—C16—H16C	109.5
N1—C3—C4	110.97 (19)	N3—C17—C18	111.3 (2)
N1—C3—H3A	109.4	N3—C17—H17A	109.4
C4—C3—H3A	109.4	C18—C17—H17A	109.4
N1—C3—H3B	109.4	N3—C17—H17B	109.4
C4—C3—H3B	109.4	C18—C17—H17B	109.4
H3A—C3—H3B	108.0	H17A—C17—H17B	108.0
C3—C4—H4A	109.5	C17—C18—H18A	109.5
C3—C4—H4B	109.5	C17—C18—H18B	109.5
H4A—C4—H4B	109.5	H18A—C18—H18B	109.5
C3—C4—H4C	109.5	C17—C18—H18C	109.5
H4A—C4—H4C	109.5	H18A—C18—H18C	109.5
H4B—C4—H4C	109.5	H18B—C18—H18C	109.5
C6—C5—H5A	109.5	N3—C19—C20	110.9 (2)
C6—C5—H5B	109.5	N3—C19—H19A	109.5
H5A—C5—H5B	109.5	C20—C19—H19A	109.5
C6—C5—H5C	109.5	N3—C19—H19B	109.5
H5A—C5—H5C	109.5	C20—C19—H19B	109.5
H5B—C5—H5C	109.5	H19A—C19—H19B	108.0
N2—C6—C5	114.4 (2)	C19—C20—H20A	109.5
N2—C6—H6A	108.7	C19—C20—H20B	109.5
C5—C6—H6A	108.7	H20A—C20—H20B	109.5
N2—C6—H6B	108.7	C19—C20—H20C	109.5
C5—C6—H6B	108.7	H20A—C20—H20C	109.5
H6A—C6—H6B	107.6	H20B—C20—H20C	109.5
C8—C7—H7A	109.5	S1—C21—S3	113.63 (12)
C8—C7—H7B	109.5	S1—C21—H21A	108.8
H7A—C7—H7B	109.5	S3—C21—H21A	108.8
C8—C7—H7C	109.5	S1—C21—H21B	108.8
H7A—C7—H7C	109.5	S3—C21—H21B	108.8
H7B—C7—H7C	109.5	H21A—C21—H21B	107.7
N2—C8—C7	112.3 (2)
C9—N1—C2—C1	67.6 (3)	C21—S3—C11—S4	2.4 (2)
C3—N1—C2—C1	−99.3 (2)	C19—N3—C12—N4	−28.4 (4)
C9—N1—C3—C4	113.2 (3)	C17—N3—C12—N4	159.7 (2)
C2—N1—C3—C4	−79.5 (3)	C19—N3—C12—C11	150.6 (2)
C9—N2—C6—C5	−116.0 (3)	C17—N3—C12—C11	−21.3 (3)
C8—N2—C6—C5	70.3 (3)	C13—N4—C12—N3	159.5 (2)
C9—N2—C8—C7	87.2 (3)	C15—N4—C12—N3	−21.0 (4)
C6—N2—C8—C7	−99.0 (2)	C13—N4—C12—C11	−19.5 (3)
C3—N1—C9—N2	−162.6 (2)	C15—N4—C12—C11	159.9 (2)
C2—N1—C9—N2	31.4 (3)	S4—C11—C12—N3	−74.9 (3)
C3—N1—C9—C10	18.7 (3)	S3—C11—C12—N3	104.8 (2)
C2—N1—C9—C10	−147.2 (2)	S4—C11—C12—N4	104.3 (2)
C8—N2—C9—N1	−161.1 (2)	S3—C11—C12—N4	−76.1 (2)
C6—N2—C9—N1	25.7 (3)	C12—N4—C13—C14	−112.1 (2)
C8—N2—C9—C10	17.6 (3)	C15—N4—C13—C14	68.4 (3)
C6—N2—C9—C10	−155.7 (2)	C12—N4—C15—C16	−53.2 (3)
N1—C9—C10—S2	74.3 (2)	C13—N4—C15—C16	126.2 (2)
N2—C9—C10—S2	−104.5 (2)	C12—N3—C17—C18	−102.5 (3)
N1—C9—C10—S1	−105.0 (2)	C19—N3—C17—C18	85.0 (3)
N2—C9—C10—S1	76.2 (2)	C12—N3—C19—C20	−60.5 (3)
C21—S1—C10—C9	−176.11 (16)	C17—N3—C19—C20	111.9 (2)
C21—S1—C10—S2	4.71 (19)	C10—S1—C21—S3	−77.21 (14)
C21—S3—C11—C12	−177.25 (16)	C11—S3—C21—S1	−73.40 (15)