Chlorotris(N,N'-dicyclohexylthiourea-S)tellurium(II) chloride, a tellurium complex with a TeClS₃ coordination sphere

During the synthesis of a series of square-planar [TeCl₂(stu)₂] complexes, where stu represents bulky di- or tetrasubstituted thio­ureas, the title compound, [TeCl{(C₆H₁₁NH)₂CS}₃]Cl or C₃₉H₇₂ClN₆S₃Te⁺·Cl^-, was the unexpected result when stu was N,N'-di­cyclo­hexyl­thio­urea. The complex is square planar, with Te-S distances of 2.5803 (4), 2.6211 (4) and 2.8214 (4) Å, and a Te-Cl distance of 2.6485 (4) Å, indicating a small trans influence of the thio­urea ligand.

S1. Comment

The expected reaction between thioureas and TeO₂ dissolved in HCl are Te⁴⁺ + 4stu + 4Cl^- = [TeCl₂(stu)₂] + (stu)₂Cl₂ (Foss & Hauge, 1959; Husebye, 1983). In the present case, a third stu ligand has displaced one of the two chloride ligands to give the [TeCl(stu)₃]Cl product, (I), where stu = (C₆H₁₁NH)₂CS. \sch

The structure of the cation in (I) is square planar, with a TeClS₃ coordination sphere. This is the first time such coordination has been observed for tellurium. The two thioureas trans to each other point up from the coordination plane, whereas the third points down. This is a conformation with a minimized steric interaction between the ligands (Fig. 1).

The SCN₂ units of the thiourea ligands are approximately planar and the SCN₂ units trans to each other (S1 and S3) form angles with the coordination plane of 67.80 (3) and 74.75 (3)°, respectively. The remaining thiourea assumes a corresponding angle of 74.31 (3)°. Angles around 70° seem to be common for trans-[TeCl₂(stu)₂] complexes (Husebye et al., 2001).

The interplanar SCN₂/SCN₂ angle is 54.69 (6)° for the two trans-related thioureas. This is a rather large angle compared with the values in the trans complexes mentioned above, which are around 13° (Husebye et al., 2001). An analogous bromide, [TeBr(stu)₃]Br, has been synthesized and its structure reported by Kumar et al. (1990). Here, stu is 1-methylimidazole-2(3H)-thione, an N,N'-dimethyl-substituted ethylenethiourea ligand. In this complex, two adjacent thioureas point to the same side of the coordination plane, whereas the third points to the opposite side. This is a geometry that brings the thiourea ligands into closer contact compared with the geometry of the present chloride analogue, but then the bulk of the thiourea ligand is smaller in the bromide.

The Te—S bond lengths in (I) vary considerably. Bonding in square planar Te^II complexes is of the three-centre four-electron (3c-4 e) type, with a bond order of 0.5. In the near linear S1—Te—S3 sequence, Te—S1 is 2.5803 (4) and Te—S3 2.8214 (4) Å. Asymmetry in two such weak and chemically equivalent bonds is not uncommon in Te^II compounds. The average bond length of 2.7009 Å is slightly longer than 2.68 Å, the average found for such 3c-4 e systems (Husebye, 1983). However, great asymmetry in the two Te—S bond lengths is often seen to give an increase in average bond lengths in linear S—Te—S systems (Husebye, 1983). It is interesting to note that the corresponding average Te—S bond length in the bromide complex with a nearly symmetric S—Te—S sequence is 2.701 Å (Kumar et al., 1990), the same value as that found in the chloride. The Te—S2 bond length in (I) is 2.6211 (4) Å and it is positioned trans to Te—Cl1, which has a bond length of 2.6485 (4) Å, indicating a weak trans influence of the N,N'-dicyclohexylthiourea ligand. However, this influence is still greater than that of the Cl^-, indicated by the shortening of the Te—S bond at the expense of the Te—Cl bond, which lengthens relative to the average found in Cl—Te—Cl 3c-4 e systems (Husebye et al., 2001).

In the ligands, the C═S bond lengths are C1═S1 1.7576 (17), C14═S2 1.7504 (14) and C27═S3 1.7336 (14) Å. These values may be compared with the corresponding length of 1.681 (20) Å found in free thioureas (Allen et al., 1987) and reflect a normal lengthening upon coordination, a long Te—S bond corresponding to a short C═S bond and vice versa. The C—N bond length within the SCN₂ group of the three thioureas has an average of 1.328 Å. This indicates partial double-bond character through transfer of charge from N to S.

The Cl^- anion is connected to the S2 thiourea by an N4—H4···Cl2 hydrogen bond. The Cl^- ligand forms an intramolecular N2—H2···Cl1 bond with the S1 thiourea; this is reflected in a small S1—C1—N2 angle of only 117.57 (13)°. There is also a possible weak intramolecular N3—H3···S3 hydrogen bond. Intermolecular N—H···Cl hydrogen bonds connect the ions into a three-dimensional network, shown in Fig. 2. Data for the hydrogen bonds are given in Table 2.

S2. Experimental

N,N'-dicyclohexylthiourea was obtained from Lancaster. The synthesis of the tellurium complex followed a modification of the literature method of Foss & Hauge (1959, 1961). TeO₂ (1.603 g, 10 mmol) was dissolved in hot concentrated HCl (20 ml). This solution was added rapidly with stirring to N,N'-dicyclohexylthiourea (9.62 g, 40 mmol) dissolved in hot 95% ethanol (110 ml). Upon cooling the resulting red-brown solution to room temperature, small yellow crystals of (I) and some red lumps formed. The latter were discarded and the rest was filtered and washed with cold ethanol to which a few drops of concentrated HCl were added [yield 6.1 g, 66.7%; m.p. 415–417 K (decomposition)]. Analysis, found: Cl 7.75, S 10.45%; calculated for C₃₉H₇₂Cl₂N₆S₃Te: Cl 7.73, S 10.49%.

S3. Refinement

All H atoms were treated as riding, with N—H = 0.88, C—H (CH) = 1.00 and C—H (CH₂) = 0.99 Å. The isotropic displacement parameters of the H atoms were fixed at 1.2U_eq of their parent atoms. The maximum residual peak was located 0.82 Å from Te.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS86 (Sheldrick, 1990); program(s) used to refine structure: SHELXTL (Sheldrick, 2001); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

	Fig. 1. The molecular structure of (I). Displacement ellipsoids are drawn at the 50% probability level and H atoms in the cyclohexyl groups have been omitted for clarity; H atoms on N are shown as small spheres of arbitrary radii.
	Fig. 2. The molecular packing in (I), with hydrogen bonds indicated by dotted lines. For clarity, only the C atoms (dotted circles) joined to the main structural unit in the cyclohexyl groups are shown [symmetry codes: (iii) 1 - x, y - 1/2, 1/2 - z; (iv) x, 1/2 - y, 1/2 + z].

Chlorotris(N,N'-dicyclohexylthiorea-S)tellurium(II) chloride

Crystal data

C39H72ClN6S3Te^+·Cl^−	Dx = 1.290 Mg m^−3
Mr = 919.71	Melting point = 415–417 K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
a = 20.1931 (5) Å	Cell parameters from 8192 reflections
b = 20.2156 (4) Å	θ = 1.7–32.9°
c = 23.1990 (4) Å	µ = 0.91 mm^−1
V = 9470.2 (3) Å^3	T = 173 K
Z = 8	Octahedron, yellow
F(000) = 3856	0.37 × 0.25 × 0.22 mm

Data collection

Bruker SMART 2K CCD diffractometer	17005 independent reflections
Radiation source: normal-focus sealed tube	10136 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
ω scans	θmax = 32.9°, θmin = 1.7°
Absorption correction: numerical (SHELXTL; Sheldrick, 2001)	h = −30→30
Tmin = 0.809, Tmax = 0.831	k = −30→29
124117 measured reflections	l = −34→33

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)] = 0.030	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.066	H-atom parameters constrained
S = 0.92	w = 1/[σ^2(Fo^2) + (0.0322P)^2] where P = (Fo^2 + 2Fc^2)/3
17005 reflections	(Δ/σ)max = 0.005
460 parameters	Δρmax = 0.47 e Å^−3
0 restraints	Δρmin = −0.29 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.

Dihedral angles from final SHELXL refinement run:

Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)

10.9408 (0.0018) x - 5.7535 (0.0020) y + 18.3469 (0.0015) z = 7.6008 (0.0015)

* 0.2023 (0.0002) S1 * -0.1688 (0.0002) S2 * 0.1771 (0.0002) S3 * -0.1652 (0.0002) Cl1 * -0.0454 (0.0002) Te

Rms deviation of fitted atoms = 0.1613

3.3802 (0.0146) x + 15.2531 (0.0060) y + 14.7214 (0.0102) z = 13.0364 (0.0083)

Angle to previous plane (with approximate e.s.d.) = 67.80 (0.03)

* 0.0033 (0.0003) S1 * -0.0122 (0.0013) C1 * 0.0045 (0.0005) N1 * 0.0044 (0.0005) N2

Rms deviation of fitted atoms = 0.0070

10.9408 (0.0018) x - 5.7535 (0.0020) y + 18.3469 (0.0015) z = 7.6008 (0.0015)

Angle to previous plane (with approximate e.s.d.) = 67.80 (0.03)

* 0.2023 (0.0002) S1 * -0.1688 (0.0002) S2 * 0.1771 (0.0002) S3 * -0.1652 (0.0002) Cl1 * -0.0454 (0.0002) Te

Rms deviation of fitted atoms = 0.1613

9.5563 (0.0129) x + 16.6390 (0.0056) y + 7.2840 (0.0130) z = 12.2906 (0.0043)

Angle to previous plane (with approximate e.s.d.) = 74.31 (0.03)

* -0.0010 (0.0003) S2 * 0.0037 (0.0012) C14 * -0.0013 (0.0004) N3 * -0.0014 (0.0005) N4

Rms deviation of fitted atoms = 0.0021

10.9408 (0.0018) x - 5.7535 (0.0020) y + 18.3469 (0.0015) z = 7.6008 (0.0015)

Angle to previous plane (with approximate e.s.d.) = 74.31 (0.03)

* 0.2023 (0.0002) S1 * -0.1688 (0.0002) S2 * 0.1771 (0.0002) S3 * -0.1652 (0.0002) Cl1 * -0.0454 (0.0002) Te

Rms deviation of fitted atoms = 0.1613

14.1347 (0.0104) x - 12.3804 (0.0140) y - 8.5232 (0.0107) z = 5.4869 (0.0114)

Angle to previous plane (with approximate e.s.d.) = 74.75 (0.03)

* 0.0006 (0.0004) S3 * -0.0021 (0.0013) C27 * 0.0007 (0.0005) N5 * 0.0007 (0.0005) N6

Rms deviation of fitted atoms = 0.0012

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
Te	0.656148 (5)	0.419956 (5)	0.152223 (4)	0.03465 (3)
S1	0.60668 (2)	0.50599 (2)	0.222202 (16)	0.04977 (11)
S2	0.558814 (19)	0.33958 (2)	0.178341 (16)	0.04086 (9)
S3	0.722615 (18)	0.31793 (2)	0.092726 (15)	0.03654 (9)
Cl1	0.74515 (2)	0.50907 (2)	0.120565 (17)	0.04852 (10)
Cl2	0.584896 (19)	0.186503 (19)	0.390211 (14)	0.03861 (8)
N1	0.50470 (7)	0.57313 (6)	0.17613 (5)	0.0422 (3)
H1A	0.4903	0.6088	0.1584	0.051*
C1	0.56897 (9)	0.56059 (8)	0.17323 (6)	0.0419 (4)
N2	0.60757 (7)	0.59019 (6)	0.13482 (6)	0.0450 (3)
H2A	0.6505	0.5897	0.1415	0.054*
C2	0.45503 (8)	0.53249 (8)	0.20658 (6)	0.0411 (4)
H2B	0.4782	0.5063	0.2371	0.049*
N3	0.65212 (6)	0.26522 (6)	0.22576 (5)	0.0385 (3)
H3A	0.6643	0.2601	0.1896	0.046*
C3	0.42358 (8)	0.48461 (9)	0.16450 (7)	0.0471 (4)
H3B	0.4582	0.4552	0.1485	0.056*
H3C	0.4038	0.5097	0.1321	0.056*
N4	0.56410 (6)	0.28963 (6)	0.28545 (5)	0.0384 (3)
H4A	0.5796	0.2596	0.3094	0.046*
C4	0.37006 (10)	0.44279 (10)	0.19335 (8)	0.0635 (5)
H4B	0.3481	0.4148	0.1640	0.076*
H4C	0.3908	0.4132	0.2222	0.076*
N5	0.69269 (6)	0.35750 (6)	−0.01440 (5)	0.0433 (3)
H5A	0.6690	0.3529	−0.0460	0.052*
C5	0.31860 (10)	0.48602 (12)	0.22278 (8)	0.0698 (6)
H5B	0.2940	0.5116	0.1934	0.084*
H5C	0.2866	0.4577	0.2436	0.084*
N6	0.63414 (7)	0.26871 (7)	0.01749 (5)	0.0473 (3)
H6A	0.6170	0.2686	−0.0174	0.057*
C6	0.35123 (11)	0.53330 (10)	0.26491 (9)	0.0688 (6)
H6B	0.3720	0.5077	0.2965	0.083*
H6C	0.3171	0.5624	0.2821	0.083*
C7	0.40392 (11)	0.57586 (9)	0.23543 (9)	0.0709 (7)
H7A	0.3827	0.6047	0.2063	0.085*
H7B	0.4258	0.6045	0.2644	0.085*
C8	0.58495 (8)	0.62394 (8)	0.08183 (6)	0.0402 (4)
H8A	0.5508	0.6576	0.0924	0.048*
C9	0.55427 (9)	0.57453 (8)	0.03950 (7)	0.0464 (4)
H9A	0.5867	0.5392	0.0308	0.056*
H9B	0.5149	0.5537	0.0573	0.056*
C10	0.53408 (9)	0.60916 (9)	−0.01627 (7)	0.0512 (4)
H10A	0.4986	0.6416	−0.0079	0.061*
H10B	0.5162	0.5761	−0.0437	0.061*
C11	0.59288 (9)	0.64478 (9)	−0.04386 (7)	0.0531 (5)
H11A	0.6264	0.6119	−0.0560	0.064*
H11B	0.5778	0.6688	−0.0786	0.064*
C12	0.62396 (9)	0.69325 (9)	−0.00183 (8)	0.0536 (5)
H12A	0.5920	0.7291	0.0066	0.064*
H12B	0.6636	0.7134	−0.0198	0.064*
C13	0.64395 (8)	0.65927 (9)	0.05464 (8)	0.0497 (4)
H13A	0.6796	0.6268	0.0469	0.060*
H13B	0.6614	0.6927	0.0819	0.060*
C14	0.59426 (7)	0.29470 (8)	0.23501 (6)	0.0349 (3)
C15	0.69785 (7)	0.24027 (8)	0.27046 (6)	0.0370 (3)
H15A	0.6733	0.2087	0.2959	0.044*
C16	0.75419 (8)	0.20343 (9)	0.24123 (8)	0.0526 (4)
H16A	0.7770	0.2334	0.2139	0.063*
H16B	0.7362	0.1656	0.2191	0.063*
C17	0.80408 (10)	0.17791 (11)	0.28630 (9)	0.0684 (6)
H17A	0.7826	0.1436	0.3104	0.082*
H17B	0.8421	0.1572	0.2663	0.082*
C18	0.82896 (9)	0.23336 (11)	0.32477 (9)	0.0674 (6)
H18A	0.8580	0.2146	0.3550	0.081*
H18B	0.8557	0.2646	0.3015	0.081*
C19	0.77275 (9)	0.27026 (10)	0.35276 (7)	0.0557 (5)
H19A	0.7906	0.3076	0.3756	0.067*
H19B	0.7488	0.2403	0.3794	0.067*
C20	0.72465 (8)	0.29678 (8)	0.30747 (7)	0.0456 (4)
H20A	0.6874	0.3196	0.3268	0.055*
H20B	0.7477	0.3293	0.2826	0.055*
C21	0.50724 (7)	0.32912 (8)	0.30557 (6)	0.0374 (3)
H21A	0.4946	0.3606	0.2742	0.045*
C22	0.44834 (8)	0.28519 (9)	0.31802 (7)	0.0464 (4)
H22A	0.4610	0.2511	0.3466	0.056*
H22B	0.4347	0.2623	0.2822	0.056*
C23	0.39024 (9)	0.32563 (10)	0.34138 (8)	0.0568 (5)
H23A	0.3743	0.3561	0.3110	0.068*
H23B	0.3534	0.2954	0.3514	0.068*
C24	0.40961 (10)	0.36528 (10)	0.39410 (8)	0.0635 (5)
H24A	0.4202	0.3348	0.4262	0.076*
H24B	0.3719	0.3933	0.4062	0.076*
C25	0.46926 (10)	0.40882 (10)	0.38163 (9)	0.0668 (6)
H25A	0.4830	0.4314	0.4176	0.080*
H25B	0.4566	0.4432	0.3533	0.080*
C26	0.52773 (9)	0.36913 (9)	0.35791 (8)	0.0528 (4)
H26A	0.5640	0.3997	0.3472	0.063*
H26B	0.5446	0.3390	0.3882	0.063*
C27	0.68024 (7)	0.31447 (8)	0.02781 (6)	0.0362 (3)
C28	0.74112 (7)	0.41152 (7)	−0.01438 (6)	0.0367 (3)
H28A	0.7480	0.4264	0.0263	0.044*
C29	0.71280 (8)	0.46861 (9)	−0.04848 (8)	0.0546 (5)
H29A	0.6711	0.4836	−0.0302	0.066*
H29B	0.7023	0.4536	−0.0880	0.066*
C30	0.76150 (9)	0.52635 (9)	−0.05136 (9)	0.0630 (5)
H30A	0.7424	0.5619	−0.0755	0.076*
H30B	0.7683	0.5443	−0.0121	0.076*
C31	0.82687 (10)	0.50572 (11)	−0.07596 (9)	0.0675 (6)
H31A	0.8580	0.5435	−0.0751	0.081*
H31B	0.8211	0.4919	−0.1166	0.081*
C32	0.85528 (9)	0.44852 (11)	−0.04109 (11)	0.0756 (7)
H32A	0.8647	0.4638	−0.0014	0.091*
H32B	0.8976	0.4341	−0.0586	0.091*
C33	0.80722 (9)	0.38965 (9)	−0.03875 (9)	0.0585 (5)
H33A	0.8008	0.3716	−0.0780	0.070*
H33B	0.8261	0.3543	−0.0143	0.070*
C34	0.60891 (8)	0.21889 (8)	0.05719 (7)	0.0404 (4)
H34A	0.6212	0.2324	0.0972	0.048*
C35	0.53411 (8)	0.21638 (8)	0.05333 (9)	0.0534 (5)
H35A	0.5209	0.2053	0.0134	0.064*
H35B	0.5156	0.2604	0.0628	0.064*
C36	0.50584 (10)	0.16501 (9)	0.09468 (10)	0.0675 (6)
H36A	0.5152	0.1787	0.1348	0.081*
H36B	0.4572	0.1628	0.0898	0.081*
C37	0.53518 (9)	0.09730 (9)	0.08417 (11)	0.0700 (6)
H37A	0.5217	0.0813	0.0456	0.084*
H37B	0.5180	0.0659	0.1133	0.084*
C38	0.61008 (10)	0.09982 (10)	0.08767 (11)	0.0725 (6)
H38A	0.6284	0.0556	0.0785	0.087*
H38B	0.6235	0.1113	0.1275	0.087*
C39	0.63862 (9)	0.15079 (9)	0.04575 (9)	0.0591 (5)
H39A	0.6873	0.1528	0.0503	0.071*
H39B	0.6288	0.1372	0.0057	0.071*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Te	0.03150 (5)	0.04802 (6)	0.02443 (4)	−0.00137 (4)	−0.00503 (4)	0.00449 (4)
S1	0.0625 (3)	0.0582 (3)	0.02862 (18)	0.0089 (2)	0.00225 (18)	−0.00049 (18)
S2	0.03182 (19)	0.0584 (3)	0.03241 (18)	−0.00061 (18)	−0.00359 (15)	0.01299 (17)
S3	0.02987 (19)	0.0475 (2)	0.03225 (17)	0.00064 (17)	−0.00586 (14)	0.00238 (16)
Cl1	0.0380 (2)	0.0654 (3)	0.0421 (2)	−0.0145 (2)	−0.00347 (16)	−0.00345 (19)
Cl2	0.03915 (19)	0.0488 (2)	0.02788 (15)	0.00325 (17)	−0.00153 (14)	0.00699 (15)
N1	0.0515 (8)	0.0399 (8)	0.0351 (6)	0.0019 (6)	0.0102 (6)	0.0044 (6)
C1	0.0535 (11)	0.0408 (9)	0.0313 (7)	0.0009 (8)	0.0067 (7)	−0.0057 (6)
N2	0.0464 (8)	0.0474 (8)	0.0412 (7)	0.0000 (6)	0.0067 (6)	0.0025 (6)
C2	0.0515 (10)	0.0415 (9)	0.0305 (7)	−0.0014 (7)	0.0065 (7)	0.0064 (6)
N3	0.0360 (7)	0.0507 (8)	0.0288 (6)	0.0055 (6)	0.0010 (5)	0.0041 (5)
C3	0.0457 (10)	0.0584 (11)	0.0371 (8)	−0.0016 (8)	0.0066 (7)	−0.0030 (7)
N4	0.0328 (7)	0.0472 (8)	0.0352 (6)	0.0067 (6)	0.0033 (5)	0.0137 (6)
C4	0.0646 (12)	0.0775 (14)	0.0483 (10)	−0.0218 (11)	0.0059 (9)	−0.0041 (10)
N5	0.0471 (8)	0.0523 (9)	0.0305 (6)	−0.0137 (7)	−0.0109 (6)	0.0037 (6)
C5	0.0503 (11)	0.1038 (18)	0.0552 (11)	−0.0003 (12)	0.0127 (9)	0.0257 (12)
N6	0.0528 (8)	0.0538 (9)	0.0355 (7)	−0.0170 (7)	−0.0109 (6)	0.0034 (6)
C6	0.0828 (15)	0.0656 (13)	0.0580 (12)	0.0075 (11)	0.0406 (11)	0.0079 (10)
C7	0.0963 (17)	0.0523 (12)	0.0643 (12)	−0.0012 (11)	0.0509 (12)	−0.0038 (9)
C8	0.0467 (9)	0.0334 (8)	0.0405 (8)	0.0028 (7)	0.0133 (7)	0.0006 (6)
C9	0.0665 (11)	0.0343 (9)	0.0384 (8)	−0.0046 (8)	0.0132 (8)	−0.0014 (7)
C10	0.0711 (12)	0.0454 (10)	0.0371 (8)	−0.0002 (9)	0.0101 (8)	−0.0006 (7)
C11	0.0668 (12)	0.0488 (11)	0.0437 (9)	0.0103 (9)	0.0196 (8)	0.0096 (8)
C12	0.0539 (11)	0.0420 (10)	0.0650 (11)	0.0014 (9)	0.0224 (9)	0.0152 (9)
C13	0.0470 (10)	0.0455 (10)	0.0566 (10)	−0.0024 (8)	0.0146 (8)	0.0061 (8)
C14	0.0328 (8)	0.0398 (9)	0.0321 (7)	−0.0031 (7)	−0.0019 (6)	0.0048 (6)
C15	0.0341 (8)	0.0406 (9)	0.0365 (7)	0.0021 (7)	0.0004 (6)	0.0106 (6)
C16	0.0476 (10)	0.0601 (12)	0.0502 (10)	0.0153 (9)	0.0065 (8)	0.0072 (9)
C17	0.0557 (12)	0.0766 (15)	0.0727 (13)	0.0312 (11)	0.0079 (10)	0.0204 (11)
C18	0.0418 (11)	0.0916 (17)	0.0689 (13)	0.0041 (10)	−0.0095 (9)	0.0272 (12)
C19	0.0464 (10)	0.0683 (13)	0.0523 (10)	−0.0061 (9)	−0.0139 (8)	0.0099 (9)
C20	0.0403 (9)	0.0483 (10)	0.0482 (9)	−0.0010 (8)	−0.0067 (7)	0.0075 (8)
C21	0.0339 (8)	0.0429 (9)	0.0352 (7)	0.0056 (7)	0.0032 (6)	0.0114 (6)
C22	0.0344 (9)	0.0550 (11)	0.0497 (9)	−0.0044 (8)	0.0004 (7)	−0.0040 (8)
C23	0.0363 (9)	0.0774 (14)	0.0566 (11)	0.0026 (9)	0.0085 (8)	0.0059 (10)
C24	0.0610 (12)	0.0832 (15)	0.0462 (10)	0.0198 (11)	0.0152 (9)	0.0048 (10)
C25	0.0728 (14)	0.0576 (13)	0.0700 (13)	0.0121 (11)	−0.0039 (11)	−0.0189 (10)
C26	0.0451 (10)	0.0457 (10)	0.0676 (12)	−0.0036 (8)	−0.0048 (8)	−0.0094 (9)
C27	0.0329 (8)	0.0432 (9)	0.0326 (7)	−0.0005 (7)	−0.0019 (6)	−0.0031 (6)
C28	0.0357 (8)	0.0426 (9)	0.0317 (7)	−0.0048 (7)	−0.0014 (6)	−0.0019 (6)
C29	0.0396 (10)	0.0565 (12)	0.0677 (12)	−0.0004 (8)	0.0008 (8)	0.0182 (9)
C30	0.0570 (12)	0.0521 (12)	0.0800 (14)	−0.0012 (9)	0.0037 (10)	0.0189 (10)
C31	0.0641 (13)	0.0747 (15)	0.0636 (12)	−0.0232 (11)	0.0189 (10)	0.0002 (11)
C32	0.0384 (11)	0.0733 (15)	0.1151 (19)	−0.0036 (10)	0.0181 (11)	−0.0105 (14)
C33	0.0435 (10)	0.0539 (12)	0.0779 (13)	0.0032 (9)	0.0089 (9)	−0.0100 (10)
C34	0.0395 (9)	0.0400 (9)	0.0416 (8)	−0.0051 (7)	−0.0043 (7)	0.0020 (7)
C35	0.0411 (10)	0.0371 (10)	0.0820 (13)	0.0053 (8)	−0.0013 (9)	0.0073 (9)
C36	0.0424 (11)	0.0504 (12)	0.1096 (17)	−0.0014 (9)	0.0146 (11)	0.0081 (11)
C37	0.0517 (12)	0.0391 (11)	0.1193 (19)	−0.0017 (9)	0.0037 (12)	0.0146 (11)
C38	0.0526 (12)	0.0464 (11)	0.1185 (19)	0.0123 (9)	−0.0041 (12)	0.0187 (12)
C39	0.0374 (10)	0.0574 (12)	0.0825 (14)	0.0085 (8)	0.0032 (9)	−0.0002 (10)

Geometric parameters (Å, º)

Te—S1	2.5803 (4)	C16—H16B	0.9900
Te—S2	2.6211 (4)	C17—C18	1.518 (3)
Te—S3	2.8214 (4)	C17—H17A	0.9900
Te—Cl1	2.6485 (4)	C17—H17B	0.9900
S1—C1	1.7576 (17)	C18—C19	1.505 (3)
N1—C1	1.324 (2)	C18—H18A	0.9900
N1—H1A	0.8800	C18—H18B	0.9900
N1—C2	1.4766 (19)	C19—C20	1.528 (2)
N2—C1	1.326 (2)	C19—H19A	0.9900
N2—C8	1.478 (2)	C19—H19B	0.9900
N2—H2A	0.8800	C20—H20A	0.9900
S2—C14	1.7504 (14)	C20—H20B	0.9900
N3—C14	1.3290 (18)	C21—C22	1.512 (2)
N3—H3A	0.8800	C21—C26	1.517 (2)
N3—C15	1.4774 (17)	C21—H21A	1.0000
S3—C27	1.7336 (14)	C22—C23	1.529 (2)
N4—C14	1.3232 (17)	C22—H22A	0.9900
N4—C21	1.4743 (19)	C22—H22B	0.9900
N4—H4A	0.8800	C23—C24	1.514 (3)
N5—C27	1.3337 (18)	C23—H23A	0.9900
N5—C28	1.4660 (19)	C23—H23B	0.9900
N5—H5A	0.8800	C24—C25	1.520 (3)
N6—C27	1.3341 (19)	C24—H24A	0.9900
N6—C34	1.4568 (19)	C24—H24B	0.9900
N6—H6A	0.8800	C25—C26	1.530 (3)
C2—C7	1.511 (2)	C25—H25A	0.9900
C2—C3	1.514 (2)	C25—H25B	0.9900
C2—H2B	1.0000	C26—H26A	0.9900
C3—C4	1.527 (2)	C26—H26B	0.9900
C3—H3B	0.9900	C28—C29	1.511 (2)
C3—H3C	0.9900	C28—C33	1.516 (2)
C4—C5	1.520 (3)	C28—H28A	1.0000
C4—H4B	0.9900	C29—C30	1.528 (2)
C4—H4C	0.9900	C29—H29A	0.9900
C5—C6	1.518 (3)	C29—H29B	0.9900
C5—H5B	0.9900	C30—C31	1.497 (3)
C5—H5C	0.9900	C30—H30A	0.9900
C6—C7	1.530 (2)	C30—H30B	0.9900
C6—H6B	0.9900	C31—C32	1.523 (3)
C6—H6C	0.9900	C31—H31A	0.9900
C7—H7A	0.9900	C31—H31B	0.9900
C7—H7B	0.9900	C32—C33	1.537 (3)
C8—C13	1.526 (2)	C32—H32A	0.9900
C8—C9	1.532 (2)	C32—H32B	0.9900
C8—H8A	1.0000	C33—H33A	0.9900
C9—C10	1.527 (2)	C33—H33B	0.9900
C9—H9A	0.9900	C34—C35	1.514 (2)
C9—H9B	0.9900	C34—C39	1.525 (2)
C10—C11	1.529 (2)	C34—H34A	1.0000
C10—H10A	0.9900	C35—C36	1.525 (2)
C10—H10B	0.9900	C35—H35A	0.9900
C11—C12	1.518 (3)	C35—H35B	0.9900
C11—H11A	0.9900	C36—C37	1.511 (3)
C11—H11B	0.9900	C36—H36A	0.9900
C12—C13	1.533 (2)	C36—H36B	0.9900
C12—H12A	0.9900	C37—C38	1.515 (3)
C12—H12B	0.9900	C37—H37A	0.9900
C13—H13A	0.9900	C37—H37B	0.9900
C13—H13B	0.9900	C38—C39	1.530 (3)
C15—C16	1.519 (2)	C38—H38A	0.9900
C15—C20	1.528 (2)	C38—H38B	0.9900
C15—H15A	1.0000	C39—H39A	0.9900
C16—C17	1.541 (2)	C39—H39B	0.9900
C16—H16A	0.9900
S1—Te—S2	88.971 (15)	C19—C18—H18B	109.3
S1—Te—S3	169.951 (12)	C17—C18—H18B	109.3
S1—Te—Cl1	88.782 (15)	H18A—C18—H18B	107.9
S2—Te—S3	90.956 (13)	C18—C19—C20	110.88 (15)
S2—Te—Cl1	174.031 (13)	C18—C19—H19A	109.5
S3—Te—Cl1	92.220 (13)	C20—C19—H19A	109.5
Te—S1—C1	100.63 (5)	C18—C19—H19B	109.5
Te—S2—C14	100.85 (5)	C20—C19—H19B	109.5
Te—S3—C27	102.70 (5)	H19A—C19—H19B	108.1
S1—C1—N1	120.81 (12)	C15—C20—C19	110.44 (14)
S1—C1—N2	117.57 (13)	C15—C20—H20A	109.6
N1—C1—N2	121.58 (15)	C19—C20—H20A	109.6
C1—N1—C2	125.70 (14)	C15—C20—H20B	109.6
C1—N1—H1A	117.1	C19—C20—H20B	109.6
C2—N1—H1A	117.1	H20A—C20—H20B	108.1
C1—N2—C8	125.82 (15)	N4—C21—C22	110.80 (13)
C1—N2—H2A	117.1	N4—C21—C26	109.25 (13)
C8—N2—H2A	117.1	C22—C21—C26	112.02 (13)
N1—C2—C7	110.67 (13)	N4—C21—H21A	108.2
N1—C2—C3	109.39 (12)	C22—C21—H21A	108.2
C7—C2—C3	111.73 (16)	C26—C21—H21A	108.2
N1—C2—H2B	108.3	C21—C22—C23	110.93 (14)
C7—C2—H2B	108.3	C21—C22—H22A	109.5
C3—C2—H2B	108.3	C23—C22—H22A	109.5
C14—N3—C15	126.10 (12)	C21—C22—H22B	109.5
C14—N3—H3A	117.0	C23—C22—H22B	109.5
C15—N3—H3A	117.0	H22A—C22—H22B	108.0
C2—C3—C4	111.60 (13)	C24—C23—C22	111.79 (15)
C2—C3—H3B	109.3	C24—C23—H23A	109.3
C4—C3—H3B	109.3	C22—C23—H23A	109.3
C2—C3—H3C	109.3	C24—C23—H23B	109.3
C4—C3—H3C	109.3	C22—C23—H23B	109.3
H3B—C3—H3C	108.0	H23A—C23—H23B	107.9
C14—N4—C21	126.62 (12)	C23—C24—C25	110.95 (15)
C14—N4—H4A	116.7	C23—C24—H24A	109.5
C21—N4—H4A	116.7	C25—C24—H24A	109.5
C5—C4—C3	111.25 (17)	C23—C24—H24B	109.5
C5—C4—H4B	109.4	C25—C24—H24B	109.5
C3—C4—H4B	109.4	H24A—C24—H24B	108.0
C5—C4—H4C	109.4	C24—C25—C26	112.12 (16)
C3—C4—H4C	109.4	C24—C25—H25A	109.2
H4B—C4—H4C	108.0	C26—C25—H25A	109.2
C27—N5—C28	127.69 (12)	C24—C25—H25B	109.2
C27—N5—H5A	116.2	C26—C25—H25B	109.2
C28—N5—H5A	116.2	H25A—C25—H25B	107.9
C6—C5—C4	110.77 (17)	C21—C26—C25	110.92 (15)
C6—C5—H5B	109.5	C21—C26—H26A	109.5
C4—C5—H5B	109.5	C25—C26—H26A	109.5
C6—C5—H5C	109.5	C21—C26—H26B	109.5
C4—C5—H5C	109.5	C25—C26—H26B	109.5
H5B—C5—H5C	108.1	H26A—C26—H26B	108.0
C27—N6—C34	127.59 (13)	S3—C27—N5	121.23 (12)
C27—N6—H6A	116.2	S3—C27—N6	121.90 (12)
C34—N6—H6A	116.2	N5—C27—N6	116.87 (13)
C5—C6—C7	111.61 (16)	N5—C28—C29	108.43 (12)
C5—C6—H6B	109.3	N5—C28—C33	111.72 (13)
C7—C6—H6B	109.3	C29—C28—C33	111.14 (14)
C5—C6—H6C	109.3	N5—C28—H28A	108.5
C7—C6—H6C	109.3	C29—C28—H28A	108.5
H6B—C6—H6C	108.0	C33—C28—H28A	108.5
C2—C7—C6	110.28 (15)	C28—C29—C30	111.27 (14)
C2—C7—H7A	109.6	C28—C29—H29A	109.4
C6—C7—H7A	109.6	C30—C29—H29A	109.4
C2—C7—H7B	109.6	C28—C29—H29B	109.4
C6—C7—H7B	109.6	C30—C29—H29B	109.4
H7A—C7—H7B	108.1	H29A—C29—H29B	108.0
N2—C8—C13	108.58 (13)	C31—C30—C29	111.80 (17)
N2—C8—C9	110.93 (12)	C31—C30—H30A	109.3
C13—C8—C9	110.86 (13)	C29—C30—H30A	109.3
N2—C8—H8A	108.8	C31—C30—H30B	109.3
C13—C8—H8A	108.8	C29—C30—H30B	109.3
C9—C8—H8A	108.8	H30A—C30—H30B	107.9
C10—C9—C8	110.63 (13)	C30—C31—C32	109.94 (16)
C10—C9—H9A	109.5	C30—C31—H31A	109.7
C8—C9—H9A	109.5	C32—C31—H31A	109.7
C10—C9—H9B	109.5	C30—C31—H31B	109.7
C8—C9—H9B	109.5	C32—C31—H31B	109.7
H9A—C9—H9B	108.1	H31A—C31—H31B	108.2
C9—C10—C11	111.30 (15)	C31—C32—C33	111.64 (17)
C9—C10—H10A	109.4	C31—C32—H32A	109.3
C11—C10—H10A	109.4	C33—C32—H32A	109.3
C9—C10—H10B	109.4	C31—C32—H32B	109.3
C11—C10—H10B	109.4	C33—C32—H32B	109.3
H10A—C10—H10B	108.0	H32A—C32—H32B	108.0
C12—C11—C10	110.86 (13)	C28—C33—C32	110.08 (15)
C12—C11—H11A	109.5	C28—C33—H33A	109.6
C10—C11—H11A	109.5	C32—C33—H33A	109.6
C12—C11—H11B	109.5	C28—C33—H33B	109.6
C10—C11—H11B	109.5	C32—C33—H33B	109.6
H11A—C11—H11B	108.1	H33A—C33—H33B	108.2
C11—C12—C13	111.62 (14)	N6—C34—C35	109.56 (13)
C11—C12—H12A	109.3	N6—C34—C39	112.11 (14)
C13—C12—H12A	109.3	C35—C34—C39	110.62 (14)
C11—C12—H12B	109.3	N6—C34—H34A	108.1
C13—C12—H12B	109.3	C35—C34—H34A	108.1
H12A—C12—H12B	108.0	C39—C34—H34A	108.1
C8—C13—C12	110.94 (14)	C34—C35—C36	111.05 (14)
C8—C13—H13A	109.5	C34—C35—H35A	109.4
C12—C13—H13A	109.5	C36—C35—H35A	109.4
C8—C13—H13B	109.5	C34—C35—H35B	109.4
C12—C13—H13B	109.5	C36—C35—H35B	109.4
H13A—C13—H13B	108.0	H35A—C35—H35B	108.0
N3—C14—N4	120.85 (13)	C37—C36—C35	111.63 (17)
S2—C14—N3	118.07 (11)	C37—C36—H36A	109.3
S2—C14—N4	121.08 (11)	C35—C36—H36A	109.3
N3—C15—C16	108.79 (12)	C37—C36—H36B	109.3
N3—C15—C20	111.13 (12)	C35—C36—H36B	109.3
C16—C15—C20	110.61 (13)	H36A—C36—H36B	108.0
N3—C15—H15A	108.8	C36—C37—C38	110.62 (16)
C16—C15—H15A	108.8	C36—C37—H37A	109.5
C20—C15—H15A	108.8	C38—C37—H37A	109.5
C15—C16—C17	110.54 (14)	C36—C37—H37B	109.5
C15—C16—H16A	109.5	C38—C37—H37B	109.5
C17—C16—H16A	109.5	H37A—C37—H37B	108.1
C15—C16—H16B	109.5	C37—C38—C39	111.39 (16)
C17—C16—H16B	109.5	C37—C38—H38A	109.3
H16A—C16—H16B	108.1	C39—C38—H38A	109.3
C18—C17—C16	111.59 (16)	C37—C38—H38B	109.3
C18—C17—H17A	109.3	C39—C38—H38B	109.3
C16—C17—H17A	109.3	H38A—C38—H38B	108.0
C18—C17—H17B	109.3	C34—C39—C38	110.44 (15)
C16—C17—H17B	109.3	C34—C39—H39A	109.6
H17A—C17—H17B	108.0	C38—C39—H39A	109.6
C19—C18—C17	111.71 (16)	C34—C39—H39B	109.6
C19—C18—H18A	109.3	C38—C39—H39B	109.6
C17—C18—H18A	109.3	H39A—C39—H39B	108.1
S2—Te—S1—C1	−102.77 (6)	C20—C15—C16—C17	56.32 (19)
Cl1—Te—S1—C1	71.70 (6)	C15—C16—C17—C18	−54.5 (2)
S3—Te—S1—C1	167.56 (9)	C16—C17—C18—C19	54.4 (2)
S1—Te—S2—C14	−92.25 (5)	C17—C18—C19—C20	−55.8 (2)
Cl1—Te—S2—C14	−160.16 (13)	N3—C15—C20—C19	−179.01 (13)
S3—Te—S2—C14	77.70 (5)	C16—C15—C20—C19	−58.06 (18)
S1—Te—S3—C27	167.79 (9)	C18—C19—C20—C15	57.5 (2)
S2—Te—S3—C27	78.29 (6)	C14—N4—C21—C22	119.06 (16)
Cl1—Te—S3—C27	−96.66 (6)	C14—N4—C21—C26	−117.05 (17)
C2—N1—C1—N2	164.29 (14)	N4—C21—C22—C23	177.54 (13)
C2—N1—C1—S1	−18.0 (2)	C26—C21—C22—C23	55.26 (18)
Te—S1—C1—N1	121.89 (12)	C21—C22—C23—C24	−55.4 (2)
Te—S1—C1—N2	−60.32 (13)	C22—C23—C24—C25	54.9 (2)
N1—C1—N2—C8	−18.4 (2)	C23—C24—C25—C26	−54.4 (2)
S1—C1—N2—C8	163.83 (12)	N4—C21—C26—C25	−177.76 (14)
C1—N1—C2—C7	141.83 (17)	C22—C21—C26—C25	−54.6 (2)
C1—N1—C2—C3	−94.65 (18)	C24—C25—C26—C21	54.1 (2)
N1—C2—C3—C4	−178.12 (14)	C28—N5—C27—N6	−179.12 (14)
C7—C2—C3—C4	−55.2 (2)	C28—N5—C27—S3	0.5 (2)
C2—C3—C4—C5	54.4 (2)	C34—N6—C27—N5	−176.22 (15)
C3—C4—C5—C6	−54.8 (2)	C34—N6—C27—S3	4.2 (2)
C4—C5—C6—C7	56.2 (2)	Te—S3—C27—N5	80.20 (13)
N1—C2—C7—C6	177.85 (16)	Te—S3—C27—N6	−100.19 (14)
C3—C2—C7—C6	55.7 (2)	C27—N5—C28—C29	−145.37 (16)
C5—C6—C7—C2	−56.5 (2)	C27—N5—C28—C33	91.81 (19)
C1—N2—C8—C13	172.13 (15)	N5—C28—C29—C30	−178.76 (15)
C1—N2—C8—C9	−65.8 (2)	C33—C28—C29—C30	−55.6 (2)
N2—C8—C9—C10	−177.28 (13)	C28—C29—C30—C31	56.2 (2)
C13—C8—C9—C10	−56.55 (19)	C29—C30—C31—C32	−56.1 (2)
C8—C9—C10—C11	56.54 (19)	C30—C31—C32—C33	56.7 (2)
C9—C10—C11—C12	−55.90 (19)	N5—C28—C33—C32	176.88 (16)
C10—C11—C12—C13	55.2 (2)	C29—C28—C33—C32	55.6 (2)
N2—C8—C13—C12	177.99 (13)	C31—C32—C33—C28	−56.5 (2)
C9—C8—C13—C12	55.89 (19)	C27—N6—C34—C35	134.77 (17)
C11—C12—C13—C8	−55.56 (19)	C27—N6—C34—C39	−102.0 (2)
C21—N4—C14—N3	167.52 (14)	N6—C34—C35—C36	−179.60 (15)
C21—N4—C14—S2	−13.2 (2)	C39—C34—C35—C36	56.3 (2)
C15—N3—C14—N4	−17.5 (2)	C34—C35—C36—C37	−56.1 (2)
C15—N3—C14—S2	163.20 (12)	C35—C36—C37—C38	55.5 (3)
Te—S2—C14—N4	126.50 (12)	C36—C37—C38—C39	−55.9 (3)
Te—S2—C14—N3	−54.17 (12)	N6—C34—C39—C38	−179.12 (15)
C14—N3—C15—C16	173.70 (15)	C35—C34—C39—C38	−56.5 (2)
C14—N3—C15—C20	−64.28 (19)	C37—C38—C39—C34	56.6 (2)
N3—C15—C16—C17	178.65 (15)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1	0.88	2.56	3.2431 (15)	135
N3—H3A···S3	0.88	2.79	3.5618 (12)	147
N1—H1A···Cl2^i	0.88	2.46	3.3007 (14)	160
N4—H4A···Cl2	0.88	2.39	3.2294 (12)	160
N5—H5A···Cl2^ii	0.88	2.39	3.2290 (13)	160
N6—H6A···Cl2^ii	0.88	2.42	3.2445 (13)	157

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