trans-Tetrachlorobis(N,N'-dimethyl­imidazolidine-2-thione)tellurium(IV), a thiourea complex of tellurium with asymmetric Te-S bonds

The structure of the title compound, [TeCl₄(C₅H₁₀N₂S)₂] or C₁₀H₂₀Cl₄N₄S₂Te, has been solved in order to study the stereochemical activity of the lone pair of electrons on Te^IV. The two crystallographically independent mol­ecules in the asymmetric unit both show a distorted octahedral coordination of the Te atom. The two Te-S bonds are trans to each other in both mol­ecules and are greatly asymmetric, with bond lengths of 2.5686 (7) versus 2.8557 (8) Å and 2.5859 (7) versus 2.8165 (9) Å. The Te-Cl bond lengths lie in the range 2.5236 (7)-2.5589 (8) Å. The asymmetric Te-S bonds and a large S-Te-Cl angle of ca 97° involving the long Te-S bonds indicate stereochemical activity of the lone pair of electrons on Te.

S1. Comment

The reaction of TeO₂ dissolved in HCl with thioureas typically results in Te^II complexes. This is caused by disproportionation reactions where Te^IV is reduced to Te^II, whereas two thioureas are oxidized to the corresponding disulfide (Husebye, 1983). The only exceptions to this rule are represented by tetramethylthiourea (tmtu; Husebye & George, 1969; Esperås et al., 1975) and benzimidazolethione (bit), a cyclic thiourea (Von Deuten et al., 1979a). The ligand benzothiazolethione (btt), related to benzimidazolethione by replacing an NH group with S, also stabilizes the resulting Te^IV complex (Von Deuten et al., 1979b). The Te^IV complexes above are octahedral with TeX₄S₂ (X is a halogen) coordination spheres. The bit complex has a cis configuration and the others are trans complexes. Of these complexes, the monoclinic trans-[TeCl₄(tmtu)₂] is the most interesting. It is greatly distorted from octahedral symmetry in a way that indicates the stereochemical activity of the lone pair of electrons on Te (Esperås et al., 1975). The other complexes are either centrosymmetric {orthorhombic trans-[TeX₄(tmtu)₂], X = Br or Cl, and trans-[TeCl₄(btt)₂]} or have a twofold rotation axis through the Te atom {cis-[TeCl₄(bit)₂]}. The lone pair of electrons in these four compounds is stereochemically inert in the sense that it seems not to occupy a site in the coordination sphere of Te. The average Te—S bond length in the three centrosymmetric thiourea compounds is 2.703 Å. To explore the lone pair activity in Te^IV complexes further, it was decided to synthesize another tetraalkylthiourea complex of Te^IV, the title complex, (I), and investigate its structure. \sch

The structure of (I), trans-[TeCl₄(dit)₂] (dit = N,N'-dimethyl-2-imidazolidinethione), is a racemic twin and has two crystallographically independent molecules in the asymmetric unit, as illustrated in Fig. 1. The two molecules are octahedral trans complexes and both show considerable distortions from ideal symmetry (Table 1). The equatorial TeCl₄ groups are planar to within 0.175 Å for molecule 1 and 0.190 Å for molecule 2. In molecule 1, the interplanar angles between TeCl₄ and the rings connected to S11 and S12 are 10.88 (15) and 17.71 (12)°, respectively. The corresponding angles in molecule 2 are 12.69 (14) and 18.77 (12)°, respectively. Superpositioning of molecules 1 and 2 reveals a difference in the orientation of the rings bonded to the S atoms. Whereas one pair of rings in molecules 1 and 2, bonded to S12 and S22, roughly coincide, the other two are related by an approximate mirror plane through S11, Te11, Cl11, Cl14 and S12. Thus, the structure of molecule 2 is related to that of molecule 1 by a rotation of approximately 170° around the Te11—S11 bond of molecule 1. The Cl14—Te11—S11—C11 and Cl24—Te21—S21—C21 torsion angles are −96.26 (10) and 97.48 (10)°, respectively. The torsion angles C11—S11—S12—C16 [78.35 (14)°] and C21—S21—S22—C26 [−79.57 (15)°] indicate that the rings in molecules 1 and 2 are in a syn-clinal relation to each other.

There is a great asymmetry of the nearly linear S—Te—S sequences, where the long Te—S bonds are close to 2.84 Å and the short bonds are close to 2.58 Å. In addition, the Cln1-Ten1-Sn1 angles (n = 1 or 2 for molecules 1 and 2, respectively) involving the longer Te—S bonds in both complexes are ca 97°, whereas `trans' to these there are Cl—Te—S angles of about 78°. The three fac-positioned ligand donor atoms, Cln1, Cln3 and Sn1, form weaker bonds to the central Te atom than the other ligand atoms, although the differences in the Te—Cl bond lengths are small (average = 0.025 Å). This may indicate some stereochemical activity by the lone pair of electrons on Te. Such activity was indicated in the related monoclinic tetramethylthiourea complex (Esperås et al., 1975). In the latter the asymmetry in the nearly linear S—Te—S sequence is less pronounced, with the long and short Te—S bonds being 2.726 (1) and 2.649 (1) Å, respectively. However, the greater asymmetry in the Te—Cl bonds and the bond angles around Te^IV in the latter complex indicate that the lone pair of electrons moves towards an equatorial position in a Ψ-pentagonal bipyramidal structure.

The bonding in octahedral Te complexes may be described by three mutually perpendicular three-centre four-electron systems, L₁—Te—L₂ (Husebye, 1983). These systems are based on the overlap of suitable ligand orbitals with the three 5p-orbitals of Te. The role of the lone pair of electrons can be seen in different ways. In the case of an `inert' pair, it does not occupy a position in the coordination polyhedron but the Te-ligand bond lengths are greater than expected and the lone pair plays an antibonding role, occupying an a_{1 g}^* antibonding orbital (Urch, 1964). Another possibility is, of course, for the lone pair to occupy a position in the coordination polyhedron fully. This is not quite the case here, but the three long fac bonds from Ten1 to Sn1, Cln1 and Cln3 may indicate a lone pair beginning to make its presence felt in a monocapped octahedral position between the three latter atoms; the asymmetry in the Te—Cl bonds is, however, small. For an octahedral molecule with seven electron pairs in the valency shell of the central atom, there is a triply degenerate stretching vibration of t_1u symmetry that could lead to a short bond with a long bond trans to it, in one of the linear three-centre systems (Burdett, 1980). This is likely to be the case here, with the stronger Ten1-Sn2 bonds on average being 0.26 Å shorter than Ten1-Sn1.

The asymmetry in Te—S bonding in molecules 1 and 2 is reflected in the S≐C bonds of the ligand, which in turn influences the C≐N bond lengths. For the long Te—S bonds, the average S≐C and C≐N bond lengths are 1.724 and 1.337 Å, respectively. For the short Te—S bonds, the corresponding lengths are 1.749 and 1.328 Å, respectively. Although they are statistically less significant for the C≐N bonds, these values agree well with those found for the [TeCl₄(tmtu)₂] complex (Esperås et al., 1975; Husebye & George, 1969). In free thioureas, C≐S = 1.681 (20) Å and C≐N = 1.346 (23) Å (Allen et al., 1987). In the uncomplexed dit ligand, these bond lengths are 1.673 (4) and 1.338 Å (averaged), respectively (Chieh & Cheung, 1983). The lengthening of the C≐S bonds and shorthening of the N≐C bonds upon complex formation illustrates the partial π-bonding and the delocalization of charge from the N atoms toward the S atoms upon formation of the Te—S bonds.

The angles and planarity of the ligands illustrate the sp² character of the C(S) and N atoms. The ligand rings connected to S11 and S21 are planar to within 0.095 Å, those connected to S12 and S22 to within 0.015 Å. This also reflects a stronger mesomeric shift of electron density from the N atoms towards S in the more planar rings, corresponding to stronger Te—S bonds from S12 and S22 as compared with S11 and S21. The interplanar ring angles are 26.06 (16)° for molecule 1 and 28.71 (16)° for molecule 2.

S2. Experimental

Tellurium dioxide (0.798 g, 5 mmol) was dissolved in hot concentrated HCl (7 ml). To this solution was added MeOH (10 ml). The ligand N,N'-dimethylimidazole-2-thione was prepared according to the literature procedures of Maier (1970) and Chieh & Cheung (1983). This ligand (2.604 g, 20 mmol) was dissolved in hot concentrated HCl (vol?) and MeOH (10 ml) was added. The two solutions were mixed while warm and a red-brown solid was formed. The product, (I), was separated by filtration and washed with MeOH and ether [yield 2.45 g, 92%; m.p. 477–479 K (decomposition)]. Recrystallization from dimethylformamide gave crystals suitable for X-ray analysis.

S3. Refinement

H atoms? The number of Friedel pairs measured was 6090.

Computing details

Data collection: SMART (Bruker, 1999); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXTL (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures

Fig. 1. A view of the two molecules in (I) with the atomic numbering scheme. Displacement ellipsoids are drawn at the 50% probability level and H atoms are shown as small spheres of arbitrary radii.

trans-Tetrachlorobis(N,N'-dimethylimidazolidine-2-thione)tellurium(IV)

Crystal data

[TeCl4(C5H10N2S)2]	? # Insert any comments here.
Mr = 529.82	Dx = 1.858 Mg m^−3
Orthorhombic, Pna21	Melting point = 477–479 K
Hall symbol: P 2c -2n	Mo Kα radiation, λ = 0.71073 Å
a = 14.2386 (9) Å	Cell parameters from 8192 reflections
b = 9.4823 (7) Å	θ = 2.3–32.4°
c = 28.063 (2) Å	µ = 2.35 mm^−1
V = 3788.8 (5) Å^3	T = 100 K
Z = 8	Plate, red-brown
F(000) = 2080	0.35 × 0.17 × 0.08 mm

Data collection

Bruker SMART 2K CCD diffractometer	12745 independent reflections
Radiation source: normal-focus sealed tube	12135 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω scans	θmax = 32.4°, θmin = 2.3°
Absorption correction: numerical (SHELXTL; Sheldrick 1997)	h = −20→20
Tmin = 0.493, Tmax = 0.843	k = −14→14
62390 measured reflections	l = −40→40

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.026	H-atom parameters constrained
wR(F^2) = 0.052	w = 1/[σ^2(Fo^2) + (0.0114P)^2 + 3.9629P] where P = (Fo^2 + 2Fc^2)/3
S = 1.18	(Δ/σ)max = 0.002
12745 reflections	Δρmax = 1.24 e Å^−3
388 parameters	Δρmin = −0.70 e Å^−3
1 restraint	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: 0.296 (10)

Special details

Experimental. ? #Insert any special details here.

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 and Mean-plane data from final SHELXL refinement run:

## DIHEDRAL ANGLES RELATING THE RINGS IN THE TWO DIFFERENT MOLECULES

78.35 (0.14) C11 - S11 - S12 - C16 − 79.57 (0.15) C21 - S21 - S22 - C26

## TWO L.-S·Q. PLANES RELATING THE SECOND RINGS IN THE TWO DIFFERENT MOLECULES ## TWO THE FIRST.

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

− 11.9113 (0.0026) x + 4.8519 (0.0029) y + 5.4969 (0.0103) z = 0.5167 (0.0024)

* −0.7628 (0.0014) S11 * 0.2862 (0.0008) S12 * −0.1672 (0.0004) Te11 * −0.1044 (0.0007) Cl11 * −0.0732 (0.0007) Cl14 * 0.8214 (0.0014) C11 0.5417 (0.0031) C16 2.3031 (0.0009) Cl12 − 2.7092 (0.0008) Cl13

Rms deviation of fitted atoms = 0.4801

- 12.0365 (0.0026) x + 4.8132 (0.0029) y − 4.6737 (0.0102) z = 1.1054 (0.0021)

* −0.7643 (0.0014) S21 * 0.2864 (0.0008) S22 * −0.1640 (0.0004) Te21 * −0.1063 (0.0007) Cl21 * −0.0709 (0.0007) Cl24 * 0.8191 (0.0014) C21 0.4802 (0.0033) C26 2.3047 (0.0009) Cl22 − 2.7121 (0.0008) Cl23

Rms deviation of fitted atoms = 0.4796

## INTERPLANAR ANGLE BETWEEN RING PLANES IN MOLECULE 1.

0.8786 (0.0224) x − 7.1515 (0.0097) y + 18.3458 (0.0333) z = 7.1122 (0.0121)

* −0.0217 (0.0018) C11 * 0.0831 (0.0020) C12 * −0.0942 (0.0019) C13 * −0.0448 (0.0019) N11 * 0.0776 (0.0018) N12 − 0.0326 (0.0056) C14 − 0.0819 (0.0053) C15 − 0.1032 (0.0046) S11

Rms deviation of fitted atoms = 0.0697

1.8077 (0.0222) x − 3.7013 (0.0131) y + 25.5895 (0.0170) z = 3.6170 (0.0098)

Angle to previous plane (with approximate e.s.d.) = 26.06 (0.16)

* 0.0136 (0.0017) C16 * 0.0095 (0.0019) C17 * −0.0025 (0.0019) C18 * −0.0144 (0.0018) N13 * −0.0061 (0.0019) N14 − 0.1768 (0.0052) C19 0.1037 (0.0053) C20 0.0637 (0.0045) S12

Rms deviation of fitted atoms = 0.0103

## INTERPLANAR ANGLE BETWEEN RING PLANES IN MOLECULE 2.

− 0.7949 (0.0218) x + 7.1544 (0.0096) y + 18.3505 (0.0328) z = 1.2794 (0.0082)

* 0.0220 (0.0017) C21 * 0.0842 (0.0019) C22 * −0.0727 (0.0019) C23 * −0.0713 (0.0018) N21 * 0.0380 (0.0019) N22 0.0675 (0.0054) C24 0.0202 (0.0053) C25 0.0960 (0.0045) S21

Rms deviation of fitted atoms = 0.0623

− 1.5364 (0.0230) x + 3.2911 (0.0140) y + 26.1433 (0.0155) z = 4.6028 (0.0141)

Angle to previous plane (with approximate e.s.d.) = 28.71 (0.16)

* −0.0139 (0.0018) C26 * −0.0029 (0.0020) C27 * −0.0042 (0.0019) C28 * 0.0101 (0.0019) N23 * 0.0110 (0.0019) N24 − 0.0258 (0.0053) C29 0.0684 (0.0051) C30 − 0.0388 (0.0047) S22

Rms deviation of fitted atoms = 0.0094

## EQUATORIAL TECL4 PLANE IN MOLECULE 1.

− 0.1629 (0.0028) x − 5.9715 (0.0016) y + 21.7965 (0.0039) z = 4.9218 (0.0011)

* −0.1701 (0.0004) Cl11 * 0.1749 (0.0004) Cl12 * 0.1668 (0.0003) Cl13 * −0.1716 (0.0004) Cl14 0.0468 (0.0004) Te11

Rms deviation of fitted atoms = 0.1708

## EQUATORIAL TeCl4 PLANE IN MOLECULE 2.

0.4537 (0.0028) x + 5.7606 (0.0016) y + 22.2725 (0.0038) z = 3.6539 (0.0010)

* 0.1841 (0.0004) Cl21 * −0.1896 (0.0004) Cl22 * −0.1807 (0.0003) Cl23 * 0.1862 (0.0004) Cl24 − 0.0311 (0.0004) Te21

Rms deviation of fitted atoms = 0.1852

## PLANE IN FIRST RING OF MOLECULE 1.

0.8786 (0.0224) x − 7.1515 (0.0097) y + 18.3458 (0.0333) z = 7.1122 (0.0121)

* −0.0217 (0.0018) C11 * 0.0831 (0.0020) C12 * −0.0942 (0.0019) C13 * −0.0448 (0.0019) N11 * 0.0776 (0.0018) N12

Rms deviation of fitted atoms = 0.0697

## EQUATORIAL TeCl4 PLANE VERSUS PLANE IN FIRST RING OF MOLECULE 1.

− 0.1629 (0.0028) x − 5.9715 (0.0016) y + 21.7965 (0.0039) z = 4.9218 (0.0011)

Angle to previous plane (with approximate e.s.d.) = 10.88 (0.15)

* −0.1701 (0.0004) Cl11 * 0.1749 (0.0004) Cl12 * 0.1668 (0.0003) Cl13 * −0.1716 (0.0004) Cl14 0.0468 (0.0004) Te11

Rms deviation of fitted atoms = 0.1708

## PLANE IN SECOND RING OF MOLECULE 1 VERSUS EQUATORIAL TeCl4 PLANE.

1.8077 (0.0222) x − 3.7013 (0.0131) y + 25.5895 (0.0170) z = 3.6170 (0.0098)

Angle to previous plane (with approximate e.s.d.) = 17.71 (0.12)

* 0.0136 (0.0017) C16 * 0.0095 (0.0019) C17 * −0.0025 (0.0019) C18 * −0.0144 (0.0018) N13 * −0.0061 (0.0019) N14

Rms deviation of fitted atoms = 0.0103

## PLANE IN FIRST RING OF MOLECULE 2.

− 0.7949 (0.0218) x + 7.1544 (0.0096) y + 18.3505 (0.0328) z = 1.2794 (0.0082)

* 0.0220 (0.0017) C21 * 0.0842 (0.0019) C22 * −0.0727 (0.0019) C23 * −0.0713 (0.0018) N21 * 0.0380 (0.0019) N22

Rms deviation of fitted atoms = 0.0623

## EQUATORIAL TeCl4 PLANE VERSUS PLANE IN FIRST RING OF MOLECULE 2.

0.4537 (0.0028) x + 5.7606 (0.0016) y + 22.2725 (0.0038) z = 3.6539 (0.0010)

Angle to previous plane (with approximate e.s.d.) = 12.69 (0.14)

* 0.1841 (0.0004) Cl21 * −0.1896 (0.0004) Cl22 * −0.1807 (0.0003) Cl23 * 0.1862 (0.0004) Cl24 − 0.0311 (0.0004) Te21

Rms deviation of fitted atoms = 0.1852

## PLANE IN SECOND RING OF MOLECULE 2 VERSUS EQUATORIAL TeCl4 PLANE.

− 1.5364 (0.0230) x + 3.2911 (0.0140) y + 26.1433 (0.0155) z = 4.6028 (0.0141)

Angle to previous plane (with approximate e.s.d.) = 18.77 (0.12)

* −0.0139 (0.0018) C26 * −0.0029 (0.0020) C27 * −0.0042 (0.0019) C28 * 0.0101 (0.0019) N23 * 0.0110 (0.0019) N24

Rms deviation of fitted atoms = 0.0094

Refinement. Refinement of F² against ALL reflections, except for 0 0 2, which was systematically in error. 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
Te11	0.102760 (11)	0.049734 (16)	0.242349 (5)	0.01306 (3)
Cl11	0.19498 (5)	0.24040 (7)	0.28532 (2)	0.01974 (12)
Cl12	−0.04698 (5)	0.15363 (7)	0.27557 (2)	0.01874 (12)
Cl13	0.25382 (5)	−0.07279 (7)	0.21541 (3)	0.02271 (13)
Cl14	0.00609 (5)	−0.10731 (7)	0.18858 (3)	0.02074 (13)
S11	0.10660 (5)	−0.14988 (8)	0.31852 (3)	0.02094 (14)
S12	0.09042 (5)	0.19911 (7)	0.16625 (3)	0.01681 (13)
C11	0.0148 (2)	−0.0866 (3)	0.35202 (10)	0.0167 (5)
N11	0.02363 (17)	0.0077 (3)	0.38712 (9)	0.0189 (5)
N12	−0.07546 (18)	−0.1241 (3)	0.34715 (9)	0.0215 (5)
C12	−0.0668 (2)	0.0367 (4)	0.40969 (12)	0.0264 (6)
H12A	−0.0783	0.1394	0.4121	0.040*
H12B	−0.0699	−0.0054	0.4419	0.040*
N13	0.09355 (17)	0.4661 (3)	0.20159 (10)	0.0186 (5)
C13	−0.1368 (2)	−0.0331 (4)	0.37618 (13)	0.0261 (7)
H13A	−0.1837	−0.0893	0.3940	0.039*
H13B	−0.1697	0.0375	0.3563	0.039*
N14	0.23302 (18)	0.3861 (3)	0.18049 (9)	0.0187 (5)
C14	0.1109 (2)	0.0654 (4)	0.40609 (13)	0.0261 (7)
H14A	0.1340	0.0045	0.4318	0.039*
H14B	0.0995	0.1603	0.4186	0.039*
H14C	0.1580	0.0701	0.3806	0.039*
C15	−0.1152 (3)	−0.2067 (4)	0.30815 (13)	0.0322 (8)
H15A	−0.1345	−0.1433	0.2824	0.048*
H15B	−0.1698	−0.2594	0.3197	0.048*
H15C	−0.0678	−0.2728	0.2962	0.048*
C16	0.1419 (2)	0.3583 (3)	0.18368 (9)	0.0153 (5)
C17	0.1573 (2)	0.5826 (3)	0.21488 (11)	0.0212 (6)
H17A	0.1552	0.6008	0.2496	0.032*
H17B	0.1410	0.6703	0.1976	0.032*
C18	0.2539 (2)	0.5272 (3)	0.19957 (14)	0.0288 (7)
H18A	0.2821	0.5884	0.1748	0.043*
H18B	0.2973	0.5214	0.2271	0.043*
C19	−0.0080 (2)	0.4812 (3)	0.20461 (11)	0.0219 (6)
H19A	−0.0372	0.4362	0.1769	0.033*
H19B	−0.0244	0.5816	0.2051	0.033*
H19C	−0.0307	0.4361	0.2338	0.033*
C20	0.3079 (2)	0.2915 (4)	0.16581 (12)	0.0259 (6)
H20A	0.2828	0.1960	0.1620	0.039*
H20B	0.3573	0.2909	0.1901	0.039*
H20C	0.3342	0.3239	0.1354	0.039*
Te21	0.138523 (11)	0.557250 (16)	0.015710 (5)	0.01283 (3)
Cl21	0.22824 (5)	0.75222 (7)	−0.02688 (2)	0.01925 (12)
Cl22	−0.01340 (5)	0.66041 (7)	−0.01499 (2)	0.01786 (12)
Cl23	0.29155 (5)	0.43233 (7)	0.03818 (3)	0.02160 (13)
Cl24	0.04532 (5)	0.39547 (7)	0.06921 (3)	0.02001 (13)
S21	0.13812 (5)	0.35895 (8)	−0.05901 (3)	0.01981 (14)
S22	0.12815 (5)	0.70077 (7)	0.09389 (3)	0.01634 (12)
C21	0.0453 (2)	0.4235 (3)	−0.09225 (9)	0.0169 (5)
N21	−0.04472 (18)	0.3872 (3)	−0.08706 (9)	0.0213 (5)
N22	0.05509 (17)	0.5172 (3)	−0.12749 (9)	0.0190 (5)
C22	−0.1059 (2)	0.4772 (4)	−0.11634 (12)	0.0237 (6)
H22A	−0.1397	0.5473	−0.0966	0.036*
H22B	−0.1521	0.4204	−0.1344	0.036*
N23	0.27336 (17)	0.8832 (3)	0.08132 (9)	0.0197 (5)
C23	−0.0352 (2)	0.5490 (4)	−0.14982 (12)	0.0260 (6)
H23A	−0.0387	0.5091	−0.1824	0.039*
H23B	−0.0461	0.6520	−0.1514	0.039*
N24	0.13501 (17)	0.9715 (3)	0.06211 (10)	0.0200 (5)
C24	−0.0842 (3)	0.3035 (4)	−0.04857 (13)	0.0328 (8)
H24A	−0.0336	0.2534	−0.0320	0.049*
H24B	−0.1288	0.2350	−0.0617	0.049*
H24C	−0.1168	0.3656	−0.0261	0.049*
C25	0.1425 (2)	0.5731 (3)	−0.14643 (12)	0.0232 (6)
H25A	0.1954	0.5187	−0.1337	0.035*
H25B	0.1491	0.6722	−0.1371	0.035*
H25C	0.1420	0.5660	−0.1813	0.035*
C26	0.1819 (2)	0.8599 (3)	0.07796 (10)	0.0164 (5)
C27	0.2963 (2)	1.0257 (3)	0.06424 (15)	0.0304 (7)
H27A	0.3385	1.0218	0.0362	0.046*
H27B	0.3266	1.0822	0.0896	0.046*
C28	0.2006 (2)	1.0870 (3)	0.05085 (11)	0.0232 (6)
H28A	0.1863	1.1722	0.0699	0.035*
H28B	0.1981	1.1115	0.0166	0.035*
C29	0.3464 (2)	0.7863 (3)	0.09644 (12)	0.0252 (6)
H29A	0.3626	0.8051	0.1298	0.038*
H29B	0.4021	0.7992	0.0764	0.038*
H29C	0.3237	0.6892	0.0933	0.038*
C30	0.0339 (2)	0.9864 (3)	0.05649 (11)	0.0204 (6)
H30A	0.0190	1.0013	0.0228	0.031*
H30B	0.0120	1.0674	0.0751	0.031*
H30C	0.0027	0.9006	0.0678	0.031*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Te11	0.01380 (7)	0.01233 (6)	0.01304 (7)	0.00043 (5)	−0.00038 (6)	−0.00010 (7)
Cl11	0.0202 (3)	0.0208 (3)	0.0182 (3)	−0.0011 (2)	−0.0039 (2)	−0.0011 (2)
Cl12	0.0185 (3)	0.0176 (3)	0.0200 (3)	0.0027 (2)	0.0018 (2)	−0.0010 (2)
Cl13	0.0175 (3)	0.0197 (3)	0.0310 (4)	0.0022 (2)	0.0033 (3)	−0.0016 (3)
Cl14	0.0218 (3)	0.0175 (3)	0.0229 (3)	−0.0002 (2)	−0.0023 (2)	−0.0040 (2)
S11	0.0261 (4)	0.0187 (3)	0.0180 (3)	0.0050 (3)	0.0049 (3)	0.0018 (3)
S12	0.0207 (3)	0.0155 (3)	0.0142 (3)	−0.0017 (2)	−0.0028 (2)	−0.0001 (2)
C11	0.0139 (13)	0.0172 (12)	0.0189 (13)	−0.0008 (9)	−0.0007 (10)	0.0023 (10)
N11	0.0126 (11)	0.0255 (12)	0.0186 (11)	0.0009 (9)	−0.0003 (8)	−0.0039 (9)
N12	0.0208 (13)	0.0217 (12)	0.0219 (12)	−0.0037 (9)	−0.0027 (9)	0.0040 (9)
C12	0.0182 (14)	0.0362 (17)	0.0249 (15)	0.0033 (12)	0.0048 (11)	−0.0010 (13)
N13	0.0169 (12)	0.0151 (11)	0.0239 (13)	−0.0003 (8)	−0.0050 (9)	0.0011 (9)
C13	0.0161 (16)	0.0320 (16)	0.0302 (17)	0.0005 (11)	0.0009 (11)	0.0101 (13)
N14	0.0175 (12)	0.0184 (11)	0.0202 (12)	−0.0001 (9)	−0.0007 (9)	0.0010 (9)
C14	0.0197 (16)	0.0304 (16)	0.0282 (17)	−0.0004 (11)	−0.0038 (11)	−0.0074 (13)
C15	0.0377 (19)	0.0295 (16)	0.0295 (17)	−0.0119 (14)	−0.0168 (15)	0.0061 (13)
C16	0.0184 (13)	0.0163 (11)	0.0110 (10)	−0.0020 (10)	−0.0021 (9)	0.0039 (9)
C17	0.0235 (14)	0.0170 (12)	0.0232 (13)	−0.0046 (10)	−0.0018 (11)	−0.0004 (10)
C18	0.0220 (15)	0.0214 (15)	0.0432 (19)	−0.0041 (11)	−0.0074 (13)	0.0037 (13)
C19	0.0184 (13)	0.0201 (13)	0.0272 (15)	−0.0008 (10)	0.0008 (11)	0.0008 (11)
C20	0.0184 (15)	0.0331 (16)	0.0263 (15)	0.0039 (12)	0.0004 (11)	0.0009 (12)
Te21	0.01326 (7)	0.01263 (6)	0.01262 (6)	0.00061 (5)	0.00023 (6)	0.00041 (7)
Cl21	0.0195 (3)	0.0205 (3)	0.0178 (3)	−0.0021 (2)	0.0029 (2)	0.0020 (2)
Cl22	0.0163 (3)	0.0176 (3)	0.0197 (3)	0.0023 (2)	−0.0026 (2)	0.0008 (2)
Cl23	0.0177 (3)	0.0199 (3)	0.0273 (3)	0.0028 (2)	−0.0025 (2)	0.0027 (3)
Cl24	0.0207 (3)	0.0171 (3)	0.0223 (3)	−0.0004 (2)	0.0015 (2)	0.0050 (2)
S21	0.0235 (4)	0.0199 (3)	0.0160 (3)	0.0040 (2)	−0.0038 (2)	−0.0017 (3)
S22	0.0191 (3)	0.0170 (3)	0.0129 (3)	−0.0017 (2)	0.0018 (2)	−0.0005 (2)
C21	0.0222 (14)	0.0159 (12)	0.0125 (11)	−0.0016 (9)	−0.0016 (9)	−0.0045 (9)
N21	0.0168 (13)	0.0252 (12)	0.0218 (12)	−0.0037 (9)	0.0040 (9)	−0.0048 (10)
N22	0.0161 (12)	0.0249 (12)	0.0158 (11)	0.0004 (9)	−0.0001 (9)	0.0033 (9)
C22	0.0152 (15)	0.0284 (15)	0.0275 (16)	0.0000 (10)	−0.0008 (11)	−0.0074 (13)
N23	0.0160 (12)	0.0235 (12)	0.0197 (11)	−0.0026 (9)	0.0000 (9)	−0.0031 (9)
C23	0.0183 (14)	0.0367 (17)	0.0229 (14)	0.0048 (12)	−0.0039 (11)	0.0017 (13)
N24	0.0196 (13)	0.0158 (10)	0.0247 (13)	0.0004 (8)	0.0050 (9)	−0.0011 (9)
C24	0.038 (2)	0.0327 (17)	0.0279 (17)	−0.0161 (15)	0.0113 (14)	−0.0043 (13)
C25	0.0189 (16)	0.0273 (15)	0.0234 (15)	−0.0012 (11)	0.0035 (11)	0.0049 (12)
C26	0.0165 (13)	0.0193 (12)	0.0136 (12)	−0.0033 (10)	0.0041 (10)	−0.0042 (9)
C27	0.0216 (16)	0.0170 (13)	0.053 (2)	−0.0043 (11)	0.0110 (14)	−0.0051 (13)
C28	0.0272 (16)	0.0165 (12)	0.0258 (14)	−0.0067 (11)	0.0062 (12)	0.0000 (10)
C29	0.0184 (14)	0.0285 (15)	0.0288 (15)	−0.0004 (11)	−0.0005 (12)	−0.0034 (12)
C30	0.0219 (15)	0.0184 (13)	0.0209 (14)	0.0045 (10)	−0.0006 (11)	−0.0007 (10)

Geometric parameters (Å, º)

Te11—Cl11	2.5392 (7)	Te21—Cl21	2.5453 (7)
Te11—Cl12	2.5270 (7)	Te21—Cl22	2.5256 (7)
Te11—Cl13	2.5589 (7)	Te21—Cl23	2.5589 (7)
Te11—Cl14	2.5276 (7)	Te21—Cl24	2.5236 (7)
Te11—S11	2.8557 (8)	Te21—S21	2.8165 (8)
Te11—S12	2.5686 (7)	Te21—S22	2.5859 (7)
S11—C11	1.718 (3)	S21—C21	1.730 (3)
S12—C16	1.747 (3)	S22—C26	1.750 (3)
C11—N11	1.337 (4)	C21—N21	1.335 (4)
C11—N12	1.341 (4)	C21—N22	1.337 (4)
N11—C14	1.459 (4)	N21—C24	1.453 (4)
N11—C12	1.460 (4)	N21—C22	1.471 (4)
N12—C15	1.460 (4)	N22—C25	1.453 (4)
N12—C13	1.473 (4)	N22—C23	1.461 (4)
C12—C13	1.522 (5)	C22—C23	1.536 (5)
N13—C16	1.331 (4)	N23—C26	1.325 (4)
N13—C19	1.455 (4)	N23—C29	1.451 (4)
N13—C17	1.477 (4)	N23—C27	1.470 (4)
N14—C16	1.328 (4)	N24—C26	1.328 (4)
N14—C20	1.453 (4)	N24—C30	1.455 (4)
N14—C18	1.472 (4)	N24—C28	1.474 (4)
C17—C18	1.535 (5)	C27—C28	1.529 (5)
Cl11—Te11—Cl13	91.66 (2)	Cl21—Te21—Cl23	91.41 (2)
Cl12—Te11—Cl11	89.06 (2)	Cl22—Te21—Cl21	89.33 (2)
Cl12—Te11—Cl13	174.40 (2)	Cl22—Te21—Cl23	173.05 (2)
Cl12—Te11—Cl14	89.45 (2)	Cl24—Te21—Cl22	89.31 (2)
Cl14—Te11—Cl11	169.94 (2)	Cl24—Te21—Cl21	170.01 (2)
Cl14—Te11—Cl13	90.80 (2)	Cl24—Te21—Cl23	91.13 (2)
Cl11—Te11—S11	96.12 (2)	Cl21—Te21—S21	97.84 (2)
Cl12—Te11—S11	89.91 (2)	Cl22—Te21—S21	90.16 (2)
Cl13—Te11—S11	84.49 (2)	Cl23—Te21—S21	82.89 (2)
Cl14—Te11—S11	93.83 (2)	Cl24—Te21—S21	92.06 (2)
Cl11—Te11—S12	92.15 (2)	Cl21—Te21—S22	92.57 (2)
Cl12—Te11—S12	91.95 (2)	Cl22—Te21—S22	92.10 (2)
Cl13—Te11—S12	93.57 (2)	Cl23—Te21—S22	94.77 (2)
Cl14—Te11—S12	77.96 (2)	Cl24—Te21—S22	77.59 (2)
S12—Te11—S11	171.55 (2)	S22—Te21—S21	169.38 (2)
C11—S11—Te11	99.41 (10)	C21—S21—Te21	99.59 (9)
C16—S12—Te11	102.41 (9)	C26—S22—Te21	102.25 (9)
N11—C11—S11	124.5 (2)	N21—C21—S21	125.7 (2)
N11—C11—N12	110.0 (3)	N21—C21—N22	110.6 (2)
N12—C11—S11	125.5 (2)	N22—C21—S21	123.7 (2)
C11—N11—C14	126.9 (3)	C21—N21—C24	126.4 (3)
C11—N11—C12	111.3 (2)	C21—N21—C22	110.9 (3)
C14—N11—C12	121.5 (3)	C24—N21—C22	120.2 (3)
C11—N12—C15	126.1 (3)	C21—N22—C25	127.0 (3)
C11—N12—C13	110.9 (3)	C21—N22—C23	111.3 (2)
C15—N12—C13	119.9 (3)	C25—N22—C23	121.4 (3)
N11—C12—C13	103.2 (3)	N21—C22—C23	102.2 (2)
C16—N13—C19	127.7 (2)	C26—N23—C29	128.3 (3)
C16—N13—C17	110.6 (2)	C26—N23—C27	110.4 (3)
C19—N13—C17	121.4 (2)	C29—N23—C27	121.2 (2)
N12—C13—C12	102.0 (2)	N22—C23—C22	102.9 (2)
C16—N14—C20	127.9 (3)	C26—N24—C30	127.7 (3)
C16—N14—C18	110.7 (2)	C26—N24—C28	110.2 (2)
C20—N14—C18	121.0 (3)	C30—N24—C28	122.1 (3)
N13—C16—S12	123.6 (2)	N23—C26—S22	123.8 (2)
N14—C16—S12	124.2 (2)	N24—C26—S22	123.6 (2)
N14—C16—N13	112.2 (2)	N23—C26—N24	112.6 (3)
N13—C17—C18	102.9 (2)	N23—C27—C28	103.4 (2)
N14—C18—C17	103.4 (2)	N24—C28—C27	103.3 (2)
Cl12—Te11—S11—C11	−6.81 (10)	Cl24—Te21—S21—C21	97.48 (10)
Cl14—Te11—S11—C11	−96.26 (10)	Cl22—Te21—S21—C21	8.17 (10)
Cl11—Te11—S11—C11	82.23 (10)	Cl21—Te21—S21—C21	−81.18 (10)
Cl13—Te11—S11—C11	173.31 (10)	Cl23—Te21—S21—C21	−171.63 (10)
S12—Te11—S11—C11	−109.58 (18)	S22—Te21—S21—C21	110.52 (15)
Cl12—Te11—S12—C16	84.49 (10)	Cl24—Te21—S22—C26	−175.63 (11)
Cl14—Te11—S12—C16	173.51 (10)	Cl22—Te21—S22—C26	−86.80 (11)
Cl11—Te11—S12—C16	−4.64 (10)	Cl21—Te21—S22—C26	2.63 (11)
Cl13—Te11—S12—C16	−96.43 (10)	Cl23—Te21—S22—C26	94.26 (11)
S11—Te11—S12—C16	−172.89 (17)	S21—Te21—S22—C26	171.03 (15)
Te11—S11—C11—N11	−91.2 (3)	Te21—S21—C21—N21	−89.7 (2)
Te11—S11—C11—N12	89.0 (3)	Te21—S21—C21—N22	91.0 (2)
N12—C11—N11—C14	174.5 (3)	N22—C21—N21—C24	−171.0 (3)
S11—C11—N11—C14	−5.3 (5)	S21—C21—N21—C24	9.7 (4)
N12—C11—N11—C12	1.6 (3)	N22—C21—N21—C22	−8.8 (3)
S11—C11—N11—C12	−178.2 (2)	S21—C21—N21—C22	171.8 (2)
N11—C11—N12—C15	169.5 (3)	N21—C21—N22—C25	−174.6 (3)
S11—C11—N12—C15	−10.6 (4)	S21—C21—N22—C25	4.8 (4)
N11—C11—N12—C13	9.3 (3)	N21—C21—N22—C23	−0.9 (3)
S11—C11—N12—C13	−170.9 (2)	S21—C21—N22—C23	178.5 (2)
C11—N11—C12—C13	−11.1 (3)	C21—N21—C22—C23	14.0 (3)
C14—N11—C12—C13	175.6 (3)	C24—N21—C22—C23	177.4 (3)
C11—N12—C13—C12	−15.5 (3)	C21—N22—C23—C22	9.5 (3)
C15—N12—C13—C12	−177.1 (3)	C25—N22—C23—C22	−176.4 (3)
N11—C12—C13—N12	15.1 (3)	N21—C22—C23—N22	−13.4 (3)
C20—N14—C16—N13	175.5 (3)	C29—N23—C26—N24	−179.0 (3)
C18—N14—C16—N13	2.1 (3)	C27—N23—C26—N24	−2.5 (4)
C20—N14—C16—S12	−4.8 (4)	C29—N23—C26—S22	2.3 (4)
C18—N14—C16—S12	−178.1 (2)	C27—N23—C26—S22	178.8 (2)
C19—N13—C16—N14	171.4 (3)	C30—N24—C26—N23	−176.4 (3)
C17—N13—C16—N14	−2.9 (3)	C28—N24—C26—N23	2.6 (3)
C19—N13—C16—S12	−8.3 (4)	C30—N24—C26—S22	2.3 (4)
C17—N13—C16—S12	177.4 (2)	C28—N24—C26—S22	−178.7 (2)
Te11—S12—C16—N14	88.4 (2)	Te21—S22—C26—N23	−88.2 (2)
Te11—S12—C16—N13	−91.8 (2)	Te21—S22—C26—N24	93.3 (2)
C16—N13—C17—C18	2.3 (3)	C26—N23—C27—C28	1.4 (3)
C19—N13—C17—C18	−172.4 (3)	C29—N23—C27—C28	178.1 (3)
C16—N14—C18—C17	−0.5 (3)	C26—N24—C28—C27	−1.6 (3)
C20—N14—C18—C17	−174.4 (3)	C30—N24—C28—C27	177.5 (3)
N13—C17—C18—N14	−1.0 (3)	N23—C27—C28—N24	0.1 (3)