Bis(3-phenyl-1,2,4-thiadiazole-5-thiolato)mercury(II)

Article abstract of DOI:10.1107/S0108270105025734

The title compound, [Hg(C₈H₅N₂S ₂)₂], has crystallographic C₂ symmetry. The Hg-S distance is 2.353 (2) A and the coordination geometry is linear, with an S-Hg-S angle of 179.77 (18)°. The exocyclic C-S single-bond distance is 1.749 (6) A, and intramolecular Hg...N distances of 2.857 (4) A exist, as well as secondary Hg...C and S...S contacts.

Full text of DOI:10.1107/S0108270105025734

metal-organic compounds
Acta Crystallographica Section C
Crystal Structure
Communications
us to obtain metal derivatives of the above-mentioned
compounds. This work describes the synthesis and crystal
structure of the ®rst example, the title compound, (I).
ISSN 0108-2701
Bis(3-phenyl-1,2,4-thiadiazole-5-thiol-
ato)mercury(II)
YaËsar Durust,a Cevher AltugÆ,a CËetin Bozkurta and Frank R.
È È
Fronczekb*
The molecular structure of (I) is illustrated in Fig. 1. The
molecule lies on a crystallographic twofold axis, and although
this does not require the coordination geometry to be strictly
linear, it is linear within experimental error. No previous
examples of complexes of 1,2,4-thiadiazol-5-ylthiolate ligands
exist in the Cambridge Structural Database (CSD, Version
5.26, November 2004 release; Allen, 2002), but the Hg1ÐS1
distance agrees well with those in two recent determinations of
bis(1,3-benzothiazole-2-thiolato)mercury(II) (CSD refcode
aDepartment of Chemistry, Faculty of Arts and Sciences, Abant Izzet Baysal
University, TR-14280 Bolu, Turkey, and bDepartment of Chemistry, Louisiana
State University, Baton Rouge, LA 70803-1804, USA
Correspondence e-mail: ffroncz@lsu.edu
Received 16 February 2005
Accepted 11 August 2005
Online 31 August 2005
The title compound, [Hg(C8H5N2S2)2], has crystallographic C2
Ê
symmetry. The HgÐS distance is 2.353 (2) A and the
coordination geometry is linear, with an SÐHgÐS angle of
179.77 (18)ꢀ. The exocyclic CÐS single-bond distance is
Ê
METZUG), viz. 2.344 (3)±2.351 (3) A for three unique values
Ê
Â
(Bell et al., 2001) and 2.338 (3)±2.345 (3) A (Popovic et al.,
2002). The mean value for HgÐS distances in HgII
arenethionate complexes in the compilation of Orpen et al.
Ê
Ê
1.749 (6) A, and intramolecular HgÁ Á ÁN distances of
Ê
(1989) is 2.362 A.
The S1ÐC1 distance is indicative of a single bond, also in
2.857 (4) A exist, as well as secondary HgÁ Á ÁC and SÁ Á ÁS
contacts.
Ê
reasonable agreemement with the mean value of 1.761 A
reported for arenethiolates by Orpen et al. (1989) and with the
values from the two determinations of METZUG [1.727 (10)±
Ê
1.751 (9) A]. Thus, the ligand is established to be a hetero-
Comment
In recent years, there has been considerable interest in the
complexes of heterocyclic thiones and oxadiazole, triazole and
related ligands (Raper, 1997; Maravalli & Goudar, 1999; Bell
et al., 2000, 2001, 2004). Aromatic nitrogen-containing
heterocyclic molecules such as diazines and azolates have
been increasingly used in a variety of bridging capacities
(Steel, 1990). The fact that mercury(II) ions interact with
many biological molecules through coordination with depro-
tonated thiol, imidazole, disul®de, thioether, amino or
carboxylate groups is well known, and a great deal of effort
has been devoted to the characterization of these interactions
cyclic thiolate. Bond distances within the 1,2,4-thiadiazole ring
are consisent with those of the only structure in the CSD
having an S atom at C1 on this heterocycle, namely 3,5-bis-
(methylmercapto)-1,2,4-thiadiazole (BICJEC; Gattow et al.,
1982), except that BICJEC has C2ÐN1 slightly longer
Ê
Ê
[1.373 (6) A] and N2ÐS2 slightly shorter [1.613 (5) A]. The
1,2,4-thiadiazole and phenyl rings of (I) are coplanar, and the
Â
in model molecules and in proteins (Popovic et al., 2000;
Kajdan et al., 2000). Interest in the structural chemistry of
mercury(II) halide complexes with ligands containing S-donor
atoms, such as heterocyclic thioamides, is related not only to
the toxicological behaviour of the metal and to the detox-
i®cation of mercury, but also to their industrial applications,
especially in semiconductors or in photovoltaic devices
(Hadjikakou et al., 2003). Extensive use of heterocyclic
thionates as bridging ligands stems from the presence of the
thioamide NÐCÐS group. Parent ligands adopt the thione
form in the solid but may exist, at least in part, as the thiol
form in solution, particularly in non-polar solvents (Cotton &
Walton, 1993).
Figure 1
The structure of (I), viewed normal to the twofold axis, showing the atom-
numbering scheme. Displacement ellipsoids are drawn at the 50%
probability level and H atoms are shown as small spheres of arbitrary
radii.
Æ
È È
Our previous reports (AgõrbasË et al., 1992; Durust et al.,
1991) related to the synthesis of the various thiadiazole deri-
vatives on the basis of thione±thiol rearrangement encouraged
m442 # 2005 International Union of Crystallography
DOI: 10.1107/S0108270105025734
Acta Cryst. (2005). C61, m442±m444

metal-organic compounds
Crystal data
[Hg(C8H5N2S2)2]
Mr = 587.11
Monoclinic, C2
Mo Kꢃ radiation
Cell parameters from 1083
re¯ections
ꢄ = 2.5±28.3ꢀ
Ê
a = 23.066 (2) A
1
Ê
b = 5.0026 (4) A
ꢅ = 9.27 mm
T = 105 K
Ê
c = 8.0220 (7) A
ꢂ = 108.871 (9)ꢀ
V = 875.90 (14) A
Z = 2
Dx = 2.226 Mg m
Lath, colourless
0.17 Â 0.05 Â 0.03 mm
3
Ê
3
Data collection
Nonius KappaCCD diffractometer
(with an Oxford Cryosystems
Cryostream Cooler)
1960 independent re¯ections
1959 re¯ections with I > 2ꢇ(I)
Rint = 0.053
ꢄmax = 28.3ꢀ
! scans with ꢆ offsets
Figure 2
A stereoview, illustrating the secondary interactions in (I). The b axis is
vertical and the SÁ Á ÁS contact lies approximately along c.
Absorption correction: multi-scan
(SCALEPACK; Otwinowski &
Minor, 1997)
Tmin = 0.355, Tmax = 0.757
4345 measured re¯ections
h = 29 ! 30
k = 5 ! 6
l = 10 ! 10
two thiadiazole rings related by the twofold axis are nearly
orthogonal, forming a dihedral angle of 88.2 (1)ꢀ. The 1,2,4-
thiadiazole ring is planar, with a maximum deviation of
Re®nement
Re®nement on F2
R[F2 > 2ꢇ(F2)] = 0.023
wR(F2) = 0.050
S = 1.04
Áꢈmax = 0.75 e A
3
Ê
3
Ê
0.84 e A
Áꢈmin
=
Ê
Ê
Extinction correction: SHELXL97
(Sheldrick, 1997)
Extinction coef®cient: 0.0030 (3)
Absolute structure: Flack (1983),
with 746 Friedel pairs
0.005 (4) A (for C1 and N1), and the Hg atom lies 0.3179 (1) A
out of this plane, such that the HgÁ Á ÁN1 distance is
1960 re¯ections
115 parameters
H-atom parameters constrained
Ê
2.857 (4) A. Similar, but slightly longer, corresponding
distances were found in the two determinations of METZUG,
w = 1/[ꢇ2(Fo
Flack parameter: 0.005 (9)
2
)
Ê
falling in the range 2.970 (8)±3.119 (8) A, and intermolecular
+ 4.7102P]
where P = (Fo2 + 2Fc )/3
(Á/ꢇ)max = 0.001
Ê
2
HgÁ Á ÁN contacts of average length 2.9 A were found in the
structure of a linear HgII aminothiolate complex (Almagro et
al., 2001).
In similar linear HgII complexes with thiolate ligands, Block
et al. (1990) and Casals et al. (1991) noted secondary HgÁ Á ÁS
interactions shorter than the sum of the van der Waals radii,
increasing the Hg coordination number. The title structure
contains none of these, but has close contacts with the phenyl
rings of the molecule related by y + 1, with the nearest distance
Table 1
Selected geometric parameters (A, ).
ꢀ
Ê
Hg1ÐS1
S1ÐC1
S2ÐN2
S2ÐC1
2.353 (2)
1.749 (6)
1.653 (5)
1.724 (5)
N1ÐC1
N1ÐC2
N2ÐC2
1.312 (7)
1.365 (6)
1.328 (7)
S1ÐHg1ÐS1i
C1ÐS1ÐHg1
N2ÐS2ÐC1
C1ÐN1ÐC2
C2ÐN2ÐS2
N1ÐC1ÐS2
179.77 (18)
92.00 (18)
92.6 (2)
109.6 (4)
107.9 (4)
111.3 (4)
N1ÐC1ÐS1
S2ÐC1ÐS1
N2ÐC2ÐN1
N2ÐC2ÐC3
N1ÐC2ÐC3
123.6 (4)
125.1 (3)
118.6 (5)
122.0 (4)
119.4 (4)
Ê
being HgÁ Á ÁC4 = 3.289 (3) A. Along with the aforementioned
intramolecular HgÁ Á ÁN contacts, these secondary interactions
complete the coordination sphere of Hg, which may be viewed
as six-coordinate (Fig. 2). Fig. 2 also shows close SÁ Á ÁS
contacts along the c direction [S1Á Á ÁS1( x, y, 1 z) =
Hg1ÐS1ÐC1ÐN1
7.1 (5)
N1ÐC2ÐC3ÐC4
1.2 (7)
Ê
3.335 (1) A], which are somewhat shorter than twice the van
Ê
der Waals radius of sulfur (1.8 A; Bondi, 1964).
Symmetry code: (i) x; y; z.
H atoms were placed in idealized positions, with CÐH distances of
Ê
0.95 A and displacement parameters assigned as Uiso(H) = 1.2Ueq(C).
Experimental
Data collection: COLLECT (Nonius, 2000); cell re®nement:
SCALEPACK (Otwinowski
DENZO (Otwinowski
A warm solution of HgCl2 (0.5 mmol, 135.7 mg) in aqueous ethanol
(10 ml) was added dropwise to a solution of 3-phenyl-1,2,4-thia-
&
Minor, 1997); data reduction:
Minor, 1997) and SCALEPACK;
&
Æ
diazole-5-thione (AgõrbasË et al., 1992) (1 mmol, 194 mg) in ethanol
program(s) used to solve structure: SIR97 (Altomare et al., 1999);
program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997);
molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); soft-
ware used to prepare material for publication: SHELXL97.
(10 ml). A white precipitate formed immediately. The reaction
mixture was re¯uxed for 2 h. The solvent was evaporated under
reduced pressure, and the crude product was recrystallized from ethyl
acetate as colourless needles (m.p. 489±492 K). RF (EtOAc±light
1
petroleum, 1:1): 0.68; H NMR (CDCl3): ꢀ 7.27±7.35 (m, 6H), 7.95±
The purchase of the diffractometer was made possible by
grant No. LEQSF (1999±2000)-ENH-TR-13, administrated by
the Louisiana Board of Regents. YD and CA are grateful to
the AIBU Research Fund (BAP grant No. 2002.03.03.121) for
support.
7.98 (m, 4H); 13C NMR (CDCl3): ꢀ 127.8, 128.6, 129.2, 130.4, 131.4; IR
(KBr, ꢁ, cm 1): 1463, 1432, 1319, 1279, 1113, 1039, 898, 781, 704.
Analysis calculated: C 32.73, H 1.72, N 9.54, S 21.85%; found: C 33.20,
H 2.21, N 9.53, S 21.66%. MS (EI, 70 eV): 592 (M+, 2), 386 (15),
283 (2), 225 (17), 219 (23), 135 (100), 122 (26), 103 (65), 77 (20).
ꢁ
Acta Cryst. (2005). C61, m442±m444
Durust et al. [Hg(C8H5N2S2)2] m443
È È

metal-organic compounds
Â
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Supplementary data for this paper are available from the IUCr electronic
archives (Reference: EM1000). Services for accessing these data are
described at the back of the journal.
È È
Æ
È
Durust, Y., AgõrbasË, H. & Sumengen, D. (1991). Phosphorus Sulfur Silicon, 62,
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Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.
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ꢁ
m444 Durust et al. [Hg(C8H5N2S2)2]
Acta Cryst. (2005). C61, m442±m444
È È