Bis(μ-N-benzyl-N-methyl­dithio­carbamato)-1:2κ3S,S′:S′;1:2κ3S:S,S′-bis­[bis­(N-benzyl-N-methyl­dithio­carbamato-κ2S,S′)thallium(III)]

Rizzoli, C.; Ramalingam, K.; Alexander, N.

doi:10.1107/S1600536808021004

metal-organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 8| August 2008| Pages m1020-m1021

doi:10.1107/S1600536808021004

Open

access

Bis(μ-N-benzyl-N-methyldithiocarbamato)-1:2κ³S,S′:S′;1:2κ³S:S,S′-bis[bis(N-benzyl-N-methyldithiocarbamato-κ²S,S′)thallium(III)]

Corrado Rizzoli,^a ^* Kuppukkannu Ramalingam ^b and Nagarajan Alexander ^b

^aDipartimento di Chimica Generale ed Inorganica, Chimica Analitica, Chimica Fisica, Viale G. P. Usberti 17/A, Universitá di Parma, I-43100 Parma, Italy, and ^bDepartment of Chemistry, Annamalai University, Annamalainagar 608 002, Tamilnadu, India
^*Correspondence e-mail: corrado.rizzoli@unipr.it

(Received 2 July 2008; accepted 7 July 2008; online 12 July 2008)

The molecule of the dinuclear title compound, [Tl₂(C₉H₁₀NS₂)₆], possesses a crystallographically imposed centre of symmetry. Each Tl^III atom is seven-coordinated by S atoms of four different dithiocarbamate anions in a distorted pentagonal-bipyramidal coordination geometry. The crystal structure is stabilized by a C—H⋯S hydrogen-bond interaction linking complex molecules into chains running parallel to the b axis. Intramolecular C—H⋯S hydrogen bonds are also present.

Related literature

For the crystal structures of Tl-dithiocarbamate complexes, see: Abrahamson et al. (1975 ); Burschka (1982 ); Casas et al. (1994 ); Griffin et al. (1980 ); Ivanov et al. (2006 ); Jennische et al. (1972 ); Kepert et al. (1978 ); Nilson & Hesse (1969 ); Pritzkow & Jennische (1975 ).

Experimental

Crystal data

[Tl₂(C₉H₁₀NS₂)₆]
M_r = 1586.57
Monoclinic, P 2₁ /c
a = 13.3326 (9) Å
b = 9.9280 (6) Å
c = 24.1379 (16) Å
β = 98.539 (2)°
V = 3159.6 (4) Å³
Z = 2
Mo Kα radiation
μ = 5.53 mm⁻¹
T = 296 (2) K
0.27 × 0.24 × 0.23 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.248, T_max = 0.282
39462 measured reflections
8268 independent reflections
5534 reflections with I > 2σ(I)
R_int = 0.040

Refinement

R[F² > 2σ(F²)] = 0.026
wR(F²) = 0.044
S = 0.94
8268 reflections
334 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.74 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Tl1—S1	2.9241 (8)
Tl1—S2	2.6210 (8)
Tl1—S3	3.0242 (8)
Tl1—S4	2.8736 (8)
Tl1—S5	2.7325 (9)
Tl1—S6	2.8109 (8)
Tl1—S3ⁱ	3.1605 (8)

S1—Tl1—S3	78.22 (2)
S4—Tl1—S3	60.32 (2)
S5—Tl1—S4	76.80 (3)
S5—Tl1—S6	64.52 (3)
S6—Tl1—S1	82.94 (2)
S2—Tl1—S3ⁱ	163.05 (2)
Symmetry code: (i) -x+1, -y, -z.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2B⋯S1	0.97	2.51	3.030 (5)	113
C11—H11A⋯S3	0.97	2.51	3.009 (3)	112
C18—H18C⋯S4	0.96	2.51	3.008 (3)	112
C20—H20B⋯S5	0.97	2.46	3.012 (4)	116
C18—H18A⋯S1ⁱⁱ	0.96	2.87	3.654 (3)	140
Symmetry code: (ii) x, y+1, z.

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ) and SCHAKAL (Keller, 1997 ); software used to prepare material for publication: SHELXL97 and PARST95 (Nardelli, 1995 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808021004/at2589sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808021004/at2589Isup2.hkl

checkCIF report

Comment top

Thallium exhibits an interesting metallorganic chemistry with formal oxidation states of +1 and +3 and various coordination polyhedra. However, at the best of our knowledge, reports on the structural characterization of thallium dithiocarbamates are scarce. As part of our ongoing study on the chemistry of a series of new dithiocarbamato-containing metal derivatives, the dinuclear title complex was synthesized and its crystal structure is reported here.

The title compound (Fig. 1) possesses a crystallographically imposed centre of symmetry. Each thallium(III) metal centre exhibits seven-coordination provided by the sulfur atoms of four dithiocarbamate anions, two of which acting as bidentate chelating ligands and two as bidentate bridging ligands. The coordination geometry can be described as distorted pentagonal bipyramidal, with atoms S1, S3, S4, S5 and S6 defining the equatorial plane, and atoms S2 and S3ⁱ occupying the apical positions [symmetry code: (i) 1 - x, -y, -z]. The Tl···Tl separation in the dinuclear complex molecule is 3.9221 (2) Å. The values of the Tl—S bond lengths involving the bidentate chelating ligands (Table 1) range from 2.6210 (8) to 2.9240 (10) Å, in agreement with those observed in other Tl-dithiocarbamato complexes (Burschka, 1982; Kepert et al., 1978; Griffin et al., 1980; Abrahamson et al., 1975; Casas et al., 1994). The Tl—S bond lengths involving the bridging S3 atom [3.0242 (8) and 3.1605 (8) Å] are consistent with the values reported in the literature for similar thallium(I) derivatives (Ivanov et al., 2006; Jennische et al., 1972; Pritzkow & Jennische, 1975; Nilson & Hesse, 1969). The C—S bond lengths within the dithiocarbamate ligands [mean value 1.714 (3) Å] fall in a rather narrow range of values suggesting a substantial delocalization of the double bond. The short values of the thioureide C—N distances [mean value 1.339 (4) Å] indicate that the electron density is delocalized over the NCS₂ groups and these bonds have a partial double bond character. In the IR spectrum of the title compound, the important stretching mode characteristic of thioureide C—N bond occurs at 1475 cm^-1. Thallium(III) possesses completely filled d orbitals whereas charge transfer (CT) is fully allowed and hence intense CT absorption is observed. Intraligand transitions of the dithiocarbamate anions are also observed along with a ligand-metal charge transfer (LMCT). The conformation of the dithiocarbamate anions is stabilized by intramolecular C—H···S hydrogen bonding interactions (Table 2). In the crystal structure (Fig. 2), dinuclear complex molecules are linked by an intermolecular C—H···S hydrogen bond (Table 2) into chains running parallel to the b axis.

Related literature top

For the crystal structures of Tl-dithiocarbamate complexes, see: Abrahamson et al. (1975); Burschka (1982); Casas et al. (1994); Griffin et al. (1980); Ivanov et al. (2006); Jennische et al. (1972); Kepert et al. (1978); Nilson & Hesse (1969); Pritzkow & Jennische (1975).

Experimental top

Benzylmethylamine (6 mmol) and carbon disulfide (6 mmol) in ethanol (5 ml) were mixed under ice-cold conditions to obtain a yellow solution of N-benzyl-N-methyldithiocarbamic acid. An aqueous solution (2 ml) of TlF3 (2 mmol) was then added with constant stirring. The resulting precipitate was filtered off and dried in air. Single crystals of the title compound suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution at room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997) and SCHAKAL (Keller, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PARST95 (Nardelli, 1995).

Figures top

	Fig. 1. View of the title dinuclear complex molecule with displacement ellipsoids drawn at the 30% probability level. Hydrogen atoms are omitted for clarity [Symmetry code: (i) = 1 - x, -y, -z].
	Fig. 2. View of the crystal packing of the title compound. Intermolecular hydrogen bonds are shown as dashed lines. H atoms not involved in hydrogen bonds are omitted for clarity. Colour codes: Tl red, S yellow, N blue, C grey and H white.

(I) top

Crystal data top

[Tl₂(C₉H₁₀NS₂)₆]	F(000) = 1560
M_r = 1586.57	D_x = 1.668 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6832 reflections
a = 13.3326 (9) Å	θ = 3.0–27.2°
b = 9.9280 (6) Å	µ = 5.53 mm⁻¹
c = 24.1379 (16) Å	T = 296 K
β = 98.539 (2)°	Block, yellow
V = 3159.6 (4) Å³	0.27 × 0.24 × 0.23 mm
Z = 2

Data collection top

Bruker SMART 1000 CCD diffractometer	8268 independent reflections
Radiation source: fine-focus sealed tube	5534 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.040
ω scans	θ_max = 29.8°, θ_min = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −18→18
T_min = 0.248, T_max = 0.282	k = −13→13
39462 measured reflections	l = −32→33

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.026	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.044	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.0165P)²] where P = (F_o² + 2F_c²)/3
8268 reflections	(Δ/σ)_max = 0.002
334 parameters	Δρ_max = 0.45 e Å⁻³
0 restraints	Δρ_min = −0.74 e Å⁻³

Crystal data top

[Tl₂(C₉H₁₀NS₂)₆]	V = 3159.6 (4) Å³
M_r = 1586.57	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 13.3326 (9) Å	µ = 5.53 mm⁻¹
b = 9.9280 (6) Å	T = 296 K
c = 24.1379 (16) Å	0.27 × 0.24 × 0.23 mm
β = 98.539 (2)°

Data collection top

Bruker SMART 1000 CCD diffractometer	8268 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	5534 reflections with I > 2σ(I)
T_min = 0.248, T_max = 0.282	R_int = 0.040
39462 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.026	0 restraints
wR(F²) = 0.044	H-atom parameters constrained
S = 0.94	Δρ_max = 0.45 e Å⁻³
8268 reflections	Δρ_min = −0.74 e Å⁻³
334 parameters

Special details top

Experimental. All H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H = 0.93–0.97 Å and U_iso(H) = 1.2 U_eq(C) or 1.5 U_eq(C) for methyl H atoms.

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 (Å²) top

	x	y	z	U_iso*/U_eq
Tl1	0.556603 (8)	−0.057237 (10)	0.075989 (4)	0.04911 (4)
S1	0.40839 (7)	−0.19940 (8)	0.13240 (4)	0.0762 (2)
S2	0.54015 (7)	0.02867 (9)	0.17692 (3)	0.0734 (2)
S3	0.36641 (6)	0.10572 (8)	0.04008 (3)	0.0615 (2)
S4	0.57292 (6)	0.22115 (8)	0.04598 (4)	0.0722 (2)
S5	0.75951 (6)	−0.00641 (8)	0.10233 (4)	0.0694 (2)
S6	0.67818 (6)	−0.28177 (8)	0.11090 (4)	0.0738 (2)
N1	0.4118 (2)	−0.0919 (3)	0.23396 (12)	0.0877 (9)
N2	0.4099 (2)	0.3649 (2)	0.05811 (9)	0.0601 (6)
N3	0.8704 (2)	−0.2290 (3)	0.10423 (13)	0.0879 (9)
C1	0.4483 (2)	−0.0902 (3)	0.18492 (12)	0.0648 (8)
C2	0.3332 (4)	−0.1872 (4)	0.24476 (18)	0.1292 (19)
H2A	0.3525	−0.2272	0.2815	0.155*
H2B	0.3285	−0.2589	0.2172	0.155*
C3	0.2298 (3)	−0.1208 (4)	0.24245 (16)	0.0900 (12)
C4	0.1609 (4)	−0.1736 (4)	0.27471 (19)	0.1262 (18)
H4	0.1788	−0.2466	0.2983	0.151*
C5	0.0658 (4)	−0.1170 (5)	0.2714 (2)	0.1196 (18)
H5	0.0189	−0.1533	0.2922	0.143*
C6	0.0401 (4)	−0.0078 (6)	0.2379 (2)	0.1240 (17)
H6	−0.0236	0.0314	0.2363	0.149*
C7	0.1084 (3)	0.0430 (4)	0.20688 (19)	0.1088 (14)
H7	0.0910	0.1174	0.1841	0.131*
C8	0.2029 (3)	−0.0138 (4)	0.20872 (17)	0.0876 (11)
H8	0.2484	0.0213	0.1868	0.105*
C9	0.4454 (3)	0.0057 (6)	0.27812 (15)	0.150 (2)
H9A	0.4107	−0.0106	0.3096	0.225*
H9B	0.4303	0.0952	0.2642	0.225*
H9C	0.5171	−0.0032	0.2896	0.225*
C10	0.4463 (2)	0.2424 (3)	0.04907 (10)	0.0550 (7)
C11	0.3016 (3)	0.3908 (3)	0.05803 (12)	0.0743 (10)
H11A	0.2627	0.3175	0.0390	0.089*
H11B	0.2828	0.4729	0.0372	0.089*
C12	0.2743 (2)	0.4050 (3)	0.11678 (13)	0.0607 (8)
C13	0.3135 (3)	0.3233 (3)	0.15949 (14)	0.0784 (10)
H13	0.3579	0.2548	0.1530	0.094*
C14	0.2885 (3)	0.3406 (4)	0.21247 (15)	0.0838 (10)
H14	0.3167	0.2842	0.2414	0.101*
C15	0.2231 (3)	0.4387 (4)	0.22273 (16)	0.0859 (11)
H15	0.2061	0.4501	0.2584	0.103*
C16	0.1829 (3)	0.5200 (4)	0.17998 (19)	0.1046 (14)
H16	0.1376	0.5874	0.1864	0.126*
C17	0.2083 (3)	0.5040 (4)	0.12737 (16)	0.0862 (11)
H17	0.1804	0.5610	0.0986	0.103*
C18	0.4749 (3)	0.4831 (3)	0.07046 (13)	0.0810 (11)
H18A	0.4547	0.5315	0.1014	0.122*
H18B	0.4686	0.5406	0.0382	0.122*
H18C	0.5442	0.4548	0.0799	0.122*
C19	0.7783 (2)	−0.1785 (3)	0.10589 (12)	0.0619 (8)
C20	0.9589 (3)	−0.1455 (4)	0.0978 (2)	0.1137 (15)
H20A	1.0093	−0.1554	0.1309	0.136*
H20B	0.9383	−0.0517	0.0952	0.136*
C21	1.0065 (3)	−0.1816 (4)	0.0468 (2)	0.0894 (11)
C22	1.1097 (3)	−0.1881 (4)	0.0502 (2)	0.0982 (12)
H22	1.1502	−0.1691	0.0841	0.118*
C23	1.1541 (5)	−0.2218 (6)	0.0053 (3)	0.139 (2)
H23	1.2244	−0.2251	0.0085	0.167*
C24	1.0969 (7)	−0.2506 (6)	−0.0441 (3)	0.167 (3)
H24	1.1272	−0.2774	−0.0746	0.201*
C25	0.9920 (6)	−0.2399 (7)	−0.0489 (3)	0.191 (3)
H25	0.9517	−0.2572	−0.0831	0.229*
C26	0.9477 (4)	−0.2037 (6)	−0.0031 (3)	0.145 (2)
H26	0.8777	−0.1945	−0.0063	0.174*
C27	0.8893 (3)	−0.3733 (4)	0.1102 (2)	0.1227 (16)
H27A	0.9593	−0.3914	0.1078	0.184*
H27B	0.8470	−0.4206	0.0809	0.184*
H27C	0.8743	−0.4029	0.1460	0.184*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Tl1	0.05321 (7)	0.04376 (6)	0.05131 (6)	0.00237 (6)	0.01089 (4)	−0.00302 (6)
S1	0.0853 (6)	0.0551 (5)	0.0967 (6)	−0.0087 (4)	0.0411 (5)	−0.0095 (5)
S2	0.0672 (6)	0.0906 (7)	0.0610 (5)	−0.0032 (5)	0.0052 (4)	−0.0268 (4)
S3	0.0613 (5)	0.0560 (4)	0.0684 (5)	0.0026 (4)	0.0135 (4)	−0.0121 (4)
S4	0.0686 (6)	0.0494 (4)	0.1041 (7)	0.0008 (4)	0.0310 (5)	0.0039 (4)
S5	0.0575 (5)	0.0601 (5)	0.0907 (6)	−0.0056 (4)	0.0118 (4)	−0.0074 (4)
S6	0.0661 (6)	0.0595 (5)	0.0983 (6)	0.0029 (4)	0.0203 (5)	0.0230 (5)
N1	0.086 (2)	0.116 (3)	0.0671 (19)	0.0459 (19)	0.0313 (16)	0.0198 (18)
N2	0.084 (2)	0.0478 (15)	0.0493 (14)	0.0118 (14)	0.0120 (13)	−0.0068 (11)
N3	0.0580 (19)	0.076 (2)	0.127 (3)	0.0062 (16)	0.0076 (17)	−0.0008 (18)
C1	0.067 (2)	0.072 (2)	0.0577 (18)	0.0242 (16)	0.0172 (16)	0.0057 (15)
C2	0.171 (5)	0.106 (3)	0.135 (4)	0.058 (3)	0.105 (4)	0.064 (3)
C3	0.113 (3)	0.065 (2)	0.109 (3)	0.006 (2)	0.072 (3)	0.000 (2)
C4	0.169 (5)	0.081 (3)	0.155 (4)	−0.001 (3)	0.114 (4)	−0.009 (3)
C5	0.132 (4)	0.097 (3)	0.152 (4)	−0.032 (3)	0.094 (4)	−0.027 (3)
C6	0.083 (3)	0.144 (4)	0.153 (5)	−0.022 (3)	0.047 (3)	−0.034 (4)
C7	0.081 (3)	0.115 (4)	0.133 (4)	0.005 (3)	0.025 (3)	0.002 (3)
C8	0.077 (3)	0.079 (3)	0.114 (3)	0.002 (2)	0.040 (2)	0.002 (2)
C9	0.117 (4)	0.282 (6)	0.050 (2)	0.074 (4)	0.009 (2)	−0.038 (3)
C10	0.073 (2)	0.0519 (17)	0.0401 (15)	0.0085 (15)	0.0079 (14)	−0.0025 (13)
C11	0.087 (3)	0.069 (2)	0.063 (2)	0.0315 (19)	0.0023 (18)	−0.0057 (16)
C12	0.062 (2)	0.0532 (18)	0.066 (2)	0.0076 (15)	0.0068 (16)	−0.0115 (15)
C13	0.103 (3)	0.063 (2)	0.070 (2)	0.025 (2)	0.016 (2)	−0.0013 (18)
C14	0.102 (3)	0.081 (3)	0.069 (2)	−0.004 (2)	0.017 (2)	0.007 (2)
C15	0.069 (2)	0.114 (3)	0.080 (2)	−0.009 (2)	0.027 (2)	−0.019 (3)
C16	0.089 (3)	0.126 (4)	0.105 (3)	0.039 (3)	0.036 (3)	−0.017 (3)
C17	0.092 (3)	0.086 (2)	0.083 (3)	0.035 (2)	0.020 (2)	−0.002 (2)
C18	0.133 (3)	0.0469 (18)	0.068 (2)	−0.003 (2)	0.033 (2)	−0.0070 (16)
C19	0.0542 (19)	0.071 (2)	0.0594 (18)	0.0083 (17)	0.0047 (15)	0.0032 (16)
C20	0.052 (2)	0.113 (3)	0.175 (4)	−0.002 (2)	0.012 (3)	−0.035 (3)
C21	0.064 (3)	0.073 (2)	0.132 (4)	−0.005 (2)	0.014 (3)	0.002 (2)
C22	0.064 (3)	0.095 (3)	0.137 (4)	0.006 (2)	0.021 (3)	0.022 (3)
C23	0.133 (5)	0.124 (4)	0.179 (6)	0.011 (4)	0.085 (5)	0.043 (4)
C24	0.238 (9)	0.129 (5)	0.161 (6)	−0.053 (6)	0.116 (7)	0.003 (5)
C25	0.223 (9)	0.207 (7)	0.145 (6)	−0.120 (7)	0.039 (6)	0.001 (5)
C26	0.102 (4)	0.170 (5)	0.158 (5)	−0.049 (4)	0.006 (4)	0.008 (4)
C27	0.093 (3)	0.086 (3)	0.188 (5)	0.038 (2)	0.017 (3)	0.032 (3)

Geometric parameters (Å, º) top

Tl1—S1	2.9241 (8)	C9—H9A	0.9600
Tl1—S2	2.6210 (8)	C9—H9B	0.9600
Tl1—S3	3.0242 (8)	C9—H9C	0.9600
Tl1—S4	2.8736 (8)	C11—C12	1.522 (4)
Tl1—S5	2.7325 (9)	C11—H11A	0.9700
Tl1—S6	2.8109 (8)	C11—H11B	0.9700
Tl1—S3ⁱ	3.1605 (8)	C12—C13	1.354 (4)
S1—C1	1.692 (3)	C12—C17	1.369 (4)
S2—C1	1.732 (3)	C13—C14	1.379 (4)
S3—C10	1.719 (3)	C13—H13	0.9300
S3—Tl1ⁱ	3.1605 (8)	C14—C15	1.354 (4)
S4—C10	1.714 (3)	C14—H14	0.9300
S5—C19	1.727 (3)	C15—C16	1.356 (5)
S6—C19	1.702 (3)	C15—H15	0.9300
N1—C1	1.345 (4)	C16—C17	1.371 (5)
N1—C9	1.461 (5)	C16—H16	0.9300
N1—C2	1.463 (5)	C17—H17	0.9300
N2—C10	1.339 (3)	C18—H18A	0.9600
N2—C18	1.463 (4)	C18—H18B	0.9600
N2—C11	1.466 (4)	C18—H18C	0.9600
N3—C19	1.332 (4)	C20—C21	1.510 (5)
N3—C27	1.459 (4)	C20—H20A	0.9700
N3—C20	1.469 (4)	C20—H20B	0.9700
C2—C3	1.522 (5)	C21—C26	1.352 (6)
C2—H2A	0.9700	C21—C22	1.368 (5)
C2—H2B	0.9700	C22—C23	1.351 (6)
C3—C8	1.354 (5)	C22—H22	0.9300
C3—C4	1.392 (5)	C23—C24	1.347 (7)
C4—C5	1.377 (6)	C23—H23	0.9300
C4—H4	0.9300	C24—C25	1.390 (8)
C5—C6	1.366 (6)	C24—H24	0.9300
C5—H5	0.9300	C25—C26	1.377 (7)
C6—C7	1.360 (5)	C25—H25	0.9300
C6—H6	0.9300	C26—H26	0.9300
C7—C8	1.374 (5)	C27—H27A	0.9600
C7—H7	0.9300	C27—H27B	0.9600
C8—H8	0.9300	C27—H27C	0.9600

S1—Tl1—S3	78.22 (2)	H9A—C9—H9C	109.5
S4—Tl1—S3	60.32 (2)	H9B—C9—H9C	109.5
S5—Tl1—S4	76.80 (3)	N2—C10—S4	120.1 (2)
S5—Tl1—S6	64.52 (3)	N2—C10—S3	120.3 (2)
S6—Tl1—S1	82.94 (2)	S4—C10—S3	119.54 (16)
S2—Tl1—S3ⁱ	163.05 (2)	N2—C11—C12	112.7 (2)
S2—Tl1—S5	86.57 (3)	N2—C11—H11A	109.0
S2—Tl1—S6	95.94 (3)	C12—C11—H11A	109.0
S2—Tl1—S4	86.63 (3)	N2—C11—H11B	109.0
S6—Tl1—S4	140.94 (2)	C12—C11—H11B	109.0
S2—Tl1—S1	64.44 (3)	H11A—C11—H11B	107.8
S5—Tl1—S1	134.02 (3)	C13—C12—C17	118.3 (3)
S4—Tl1—S1	131.55 (2)	C13—C12—C11	122.4 (3)
S2—Tl1—S3	84.84 (2)	C17—C12—C11	119.3 (3)
S5—Tl1—S3	136.63 (2)	C12—C13—C14	120.8 (3)
S6—Tl1—S3	158.72 (2)	C12—C13—H13	119.6
S5—Tl1—S3ⁱ	78.10 (2)	C14—C13—H13	119.6
S6—Tl1—S3ⁱ	84.05 (2)	C15—C14—C13	120.7 (3)
S4—Tl1—S3ⁱ	82.89 (2)	C15—C14—H14	119.7
S1—Tl1—S3ⁱ	132.08 (2)	C13—C14—H14	119.7
S3—Tl1—S3ⁱ	101.319 (18)	C14—C15—C16	118.8 (3)
C1—S1—Tl1	83.15 (11)	C14—C15—H15	120.6
C1—S2—Tl1	92.29 (10)	C16—C15—H15	120.6
C10—S3—Tl1	84.77 (10)	C15—C16—C17	120.8 (4)
C10—S3—Tl1ⁱ	87.45 (9)	C15—C16—H16	119.6
Tl1—S3—Tl1ⁱ	78.681 (18)	C17—C16—H16	119.6
C10—S4—Tl1	89.75 (10)	C12—C17—C16	120.7 (4)
C19—S5—Tl1	87.73 (10)	C12—C17—H17	119.7
C19—S6—Tl1	85.68 (10)	C16—C17—H17	119.7
C1—N1—C9	121.5 (4)	N2—C18—H18A	109.5
C1—N1—C2	121.8 (3)	N2—C18—H18B	109.5
C9—N1—C2	116.7 (3)	H18A—C18—H18B	109.5
C10—N2—C18	122.9 (3)	N2—C18—H18C	109.5
C10—N2—C11	122.6 (3)	H18A—C18—H18C	109.5
C18—N2—C11	114.4 (2)	H18B—C18—H18C	109.5
C19—N3—C27	120.9 (3)	N3—C19—S6	120.8 (2)
C19—N3—C20	123.3 (3)	N3—C19—S5	119.9 (2)
C27—N3—C20	115.8 (3)	S6—C19—S5	119.32 (17)
N1—C1—S1	122.4 (3)	N3—C20—C21	113.2 (3)
N1—C1—S2	117.4 (3)	N3—C20—H20A	108.9
S1—C1—S2	120.11 (17)	C21—C20—H20A	108.9
N1—C2—C3	112.5 (3)	N3—C20—H20B	108.9
N1—C2—H2A	109.1	C21—C20—H20B	108.9
C3—C2—H2A	109.1	H20A—C20—H20B	107.8
N1—C2—H2B	109.1	C26—C21—C22	119.4 (5)
C3—C2—H2B	109.1	C26—C21—C20	120.4 (4)
H2A—C2—H2B	107.8	C22—C21—C20	120.2 (4)
C8—C3—C4	119.6 (4)	C23—C22—C21	121.2 (5)
C8—C3—C2	121.3 (3)	C23—C22—H22	119.4
C4—C3—C2	119.1 (4)	C21—C22—H22	119.4
C5—C4—C3	119.4 (4)	C24—C23—C22	120.3 (6)
C5—C4—H4	120.3	C24—C23—H23	119.8
C3—C4—H4	120.3	C22—C23—H23	119.8
C6—C5—C4	120.4 (4)	C23—C24—C25	119.2 (7)
C6—C5—H5	119.8	C23—C24—H24	120.4
C4—C5—H5	119.8	C25—C24—H24	120.4
C7—C6—C5	119.4 (5)	C26—C25—C24	119.9 (7)
C7—C6—H6	120.3	C26—C25—H25	120.1
C5—C6—H6	120.3	C24—C25—H25	120.1
C6—C7—C8	121.1 (5)	C21—C26—C25	119.8 (6)
C6—C7—H7	119.5	C21—C26—H26	120.1
C8—C7—H7	119.5	C25—C26—H26	120.1
C3—C8—C7	120.0 (4)	N3—C27—H27A	109.5
C3—C8—H8	120.0	N3—C27—H27B	109.5
C7—C8—H8	120.0	H27A—C27—H27B	109.5
N1—C9—H9A	109.5	N3—C27—H27C	109.5
N1—C9—H9B	109.5	H27A—C27—H27C	109.5
H9A—C9—H9B	109.5	H27B—C27—H27C	109.5
N1—C9—H9C	109.5

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···S1	0.97	2.51	3.030 (5)	113
C11—H11A···S3	0.97	2.51	3.009 (3)	112
C18—H18C···S4	0.96	2.51	3.008 (3)	112
C20—H20B···S5	0.97	2.46	3.012 (4)	116
C18—H18A···S1ⁱⁱ	0.96	2.87	3.654 (3)	140

Symmetry code: (ii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	[Tl₂(C₉H₁₀NS₂)₆]
M_r	1586.57
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	13.3326 (9), 9.9280 (6), 24.1379 (16)
β (°)	98.539 (2)
V (Å³)	3159.6 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	5.53
Crystal size (mm)	0.27 × 0.24 × 0.23

Data collection
Diffractometer	Bruker SMART 1000 CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.248, 0.282
No. of measured, independent and observed [I > 2σ(I)] reflections	39462, 8268, 5534
R_int	0.040
(sin θ/λ)_max (Å⁻¹)	0.699

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.026, 0.044, 0.94
No. of reflections	8268
No. of parameters	334
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.45, −0.74

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SIR97 (Altomare et al., 1999), ORTEP-3 for Windows (Farrugia, 1997) and SCHAKAL (Keller, 1997), SHELXL97 (Sheldrick, 2008) and PARST95 (Nardelli, 1995).

Selected geometric parameters (Å, º) top

Tl1—S1	2.9241 (8)	Tl1—S5	2.7325 (9)
Tl1—S2	2.6210 (8)	Tl1—S6	2.8109 (8)
Tl1—S3	3.0242 (8)	Tl1—S3ⁱ	3.1605 (8)
Tl1—S4	2.8736 (8)

S1—Tl1—S3	78.22 (2)	S5—Tl1—S6	64.52 (3)
S4—Tl1—S3	60.32 (2)	S6—Tl1—S1	82.94 (2)
S5—Tl1—S4	76.80 (3)	S2—Tl1—S3ⁱ	163.05 (2)

Symmetry code: (i) −x+1, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2B···S1	0.97	2.51	3.030 (5)	113.2
C11—H11A···S3	0.97	2.51	3.009 (3)	111.6
C18—H18C···S4	0.96	2.51	3.008 (3)	112.4
C20—H20B···S5	0.97	2.46	3.012 (4)	116.1
C18—H18A···S1ⁱⁱ	0.96	2.87	3.654 (3)	140.0

Symmetry code: (ii) x, y+1, z.

References

Abrahamson, H., Heiman, J. R. & Pignolet, L. H. (1975). Inorg. Chem. 14, 2070–2075. CSD CrossRef CAS Web of Science Google Scholar
Altomare, A., Burla, M. C., Camalli, M., Cascarano, G. L., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115–119. Web of Science CrossRef CAS IUCr Journals Google Scholar
Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Burschka, C. H. (1982). Z. Anorg. Allg. Chem. 485, 217–224. CSD CrossRef CAS Web of Science Google Scholar
Casas, J. S., Castaño, M. V., Freire, C., Sanchez, A., Sordo, J., Castellano, E. E. & Zukerman-Schpector, J. (1994). Inorg. Chim. Acta, 216, 15–20. CSD CrossRef CAS Web of Science Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Griffin, R. T., Henrick, K., Matthews, R. W. & McPartlin, M. (1980). J. Chem. Soc. Dalton Trans. pp. 1550–1555. CSD CrossRef Web of Science Google Scholar
Ivanov, A. V., Bredyuk, O. A., Gerasimenko, A. V., Lutsenko, I. A., Antsutkin, O. N. & Forsling, W. (2006). Koord. Khim. 32, 354–364. CrossRef Google Scholar
Jennische, P., Olin, A. & Hesse, R. (1972). Acta Chem. Scand. A26, 2799–2812. CrossRef Web of Science Google Scholar
Keller, E. (1997). SCHAKAL97. University of Freiburg, Germany. Google Scholar
Kepert, D. L., Raston, C. L., Roberts, N. K. & White, A. H. (1978). Aust. J. Chem. 31, 1927–1932. CrossRef CAS Google Scholar
Nardelli, M. (1995). J. Appl. Cryst. 28, 659. CrossRef IUCr Journals Google Scholar
Nilson, L. & Hesse, R. (1969). Acta Chem. Scand. A23, 1951–1965. CrossRef Web of Science Google Scholar
Pritzkow, H. & Jennische, P. (1975). Acta Chem. Scand. A29, 60–70. CrossRef CAS Web of Science Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 64| Part 8| August 2008| Pages m1020-m1021

doi:10.1107/S1600536808021004

Open

access

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page

metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)