Two-dimensional polymeric [Hg(4)(μ(2)-I)(6)I(2)(μ(2)-C(4)S(6))](n).

The title compound, poly[(μ(2)-2H,5H-1,3-dithiolo[4,5-d][1,3]di-thiole-2,5-dithione)hexa-μ(2)-iodido-diiodidotetra-mercury(II)], [Hg(4)I(8)(C(4)S(6))](n), represents the first example of a coordination polymer assembled by the α,α-C(4)S(6) dithione ligand. The Hg(II) ions are four-coordinated in a distorted tetra-hedral geometry, the coordination demand being satisfied either by four bridging iodide ligands or by three iodide ligands (one terminal and two bridging) and a thio-carbonyl S atom. Due to the bridging nature of the dithione ligand, the coordination polymer has a two-dimensional structure, built up of undulated layers parallel to (001). There is an inversion center at the mid-point of the central C=C double bond.

Related literature

For the synthesis and structure of the α,α-C4S6 ligand, see: Krug et al. (1977 ▶); Beck et al. (2006 ▶). For related studies on polymeric binary carbon sulfides, see: Galloway et al. (1994 ▶). For the synthesis and structures of coordination polymers with sulfur-rich ligands, see: Peindy et al. (2005 ▶); Hameau et al. (2006 ▶); Ndiaye et al. (2007 ▶); Guyon et al. (2008 ▶).

Experimental

Crystal data

[Hg4I8(C4S6)]

M = 1028.98

Monoclinic,

a = 8.5502 (6) Å

b = 11.2156 (8) Å

c = 13.4634 (9) Å

β = 91.343 (1)°

V = 1290.73 (16) Å3

Z = 4

Mo Kα radiation

μ = 33.76 mm−1

T = 173 K

0.30 × 0.10 × 0.10 mm

Data collection

Bruker APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1999 ▶) T min = 0.035, T max = 0.133

24415 measured reflections

2543 independent reflections

2337 reflections with I > 2σ(I)

R int = 0.086

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.114

S = 1.03

2543 reflections

100 parameters

Δρmax = 3.56 e Å−3

Δρmin = −3.29 e Å−3

Data collection: SMART (Bruker, 2001 ▶); cell refinement: SAINT-Plus (Bruker, 1999 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811006556/fi2103sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811006556/fi2103Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

[Hg4I8(C4S6)]	F(000) = 1728
Mr = 1028.98	Dx = 5.295 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 8987 reflections
a = 8.5502 (6) Å	θ = 2.4–26°
b = 11.2156 (8) Å	µ = 33.76 mm−1
c = 13.4634 (9) Å	T = 173 K
β = 91.343 (1)°	Needle, dark red
V = 1290.73 (16) Å3	0.30 × 0.10 × 0.10 mm
Z = 4

Bruker APEX CCD diffractometer	2543 independent reflections
Radiation source: fine-focus sealed tube	2337 reflections with I > 2σ(I)
graphite	Rint = 0.086
ω scans	θmax = 26.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Bruker, 1999)	h = −10→10
Tmin = 0.035, Tmax = 0.133	k = −13→13
24415 measured reflections	l = −16→16

Refinement on F2	0 restraints
Least-squares matrix: full	Primary atom site location: structure-invariant direct methods
R[F2 > 2σ(F2)] = 0.039	Secondary atom site location: difference Fourier map
wR(F2) = 0.114	w = 1/[σ2(Fo2) + (0.077P)2 + 7.1937P] where P = (Fo2 + 2Fc2)/3
S = 1.03	(Δ/σ)max = 0.001
2543 reflections	Δρmax = 3.56 e Å−3
100 parameters	Δρmin = −3.29 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq
C1	0.0263 (12)	0.9542 (9)	1.0288 (7)	0.029 (2)
C2	0.2439 (12)	0.9942 (9)	0.9076 (8)	0.033 (2)
Hg1	0.51629 (6)	0.77041 (5)	0.83365 (5)	0.05585 (19)
Hg2	0.22624 (7)	0.46970 (6)	0.97826 (5)	0.0672 (2)
I1	0.82359 (9)	0.77867 (6)	0.83985 (5)	0.0374 (2)
I2	0.25603 (8)	0.64475 (6)	0.79810 (5)	0.0372 (2)
I3	0.08558 (9)	0.60123 (6)	1.11662 (5)	0.03616 (19)
I4	0.45656 (8)	0.32667 (6)	0.92556 (5)	0.03444 (19)
S1	0.2076 (3)	0.8973 (2)	1.0033 (2)	0.0374 (6)
S2	0.4123 (3)	0.9968 (3)	0.8465 (2)	0.0427 (6)
S3	−0.0987 (3)	0.9043 (2)	1.1185 (2)	0.0363 (6)

	U11	U22	U33	U12	U13	U23
C1	0.025 (5)	0.035 (5)	0.028 (5)	−0.001 (4)	0.003 (4)	0.002 (4)
C2	0.031 (5)	0.029 (5)	0.039 (5)	−0.002 (4)	0.003 (4)	−0.001 (4)
Hg1	0.0325 (3)	0.0672 (4)	0.0682 (4)	−0.0029 (2)	0.0078 (2)	0.0044 (3)
Hg2	0.0477 (4)	0.0668 (4)	0.0881 (5)	0.0157 (3)	0.0243 (3)	−0.0110 (3)
I1	0.0303 (4)	0.0452 (4)	0.0369 (4)	−0.0012 (3)	0.0048 (3)	−0.0032 (3)
I2	0.0332 (4)	0.0424 (4)	0.0359 (4)	−0.0019 (3)	0.0013 (3)	0.0038 (3)
I3	0.0351 (4)	0.0365 (4)	0.0369 (4)	−0.0014 (3)	0.0029 (3)	−0.0047 (3)
I4	0.0305 (4)	0.0404 (4)	0.0326 (4)	0.0048 (3)	0.0041 (3)	−0.0024 (3)
S1	0.0310 (14)	0.0406 (14)	0.0410 (14)	0.0074 (11)	0.0101 (11)	0.0073 (11)
S2	0.0350 (15)	0.0365 (13)	0.0576 (17)	0.0020 (11)	0.0205 (13)	0.0038 (12)
S3	0.0339 (14)	0.0372 (13)	0.0383 (13)	0.0051 (10)	0.0128 (11)	0.0067 (11)

C1—C1i	1.36 (2)	Hg1—S2	2.697 (3)
C1—S1	1.718 (11)	Hg2—I4	2.6496 (9)
C1—S3	1.724 (11)	Hg2—I3	2.6828 (9)
C2—S2	1.675 (11)	Hg2—I3ii	3.0353 (10)
C2—S3i	1.715 (11)	Hg2—I2	3.1357 (10)
C2—S1	1.720 (11)	I3—Hg2ii	3.0353 (10)
Hg1—I1	2.6285 (9)	S3—C2i	1.715 (11)
Hg1—I2	2.6678 (9)
C1i—C1—S1	117.1 (11)	I4—Hg2—I3ii	112.31 (3)
C1i—C1—S3	116.3 (11)	I3—Hg2—I3ii	91.87 (3)
S1—C1—S3	126.6 (6)	I4—Hg2—I2	95.60 (3)
S2—C2—S3i	121.0 (6)	I3—Hg2—I2	103.81 (3)
S2—C2—S1	123.4 (6)	I3ii—Hg2—I2	85.70 (3)
S3i—C2—S1	115.5 (6)	Hg1—I2—Hg2	105.93 (3)
I1—Hg1—I2	148.57 (3)	Hg2—I3—Hg2ii	88.13 (3)
I1—Hg1—S2	107.19 (7)	C1—S1—C2	95.4 (5)
I2—Hg1—S2	103.53 (7)	C2—S2—Hg1	107.7 (4)
I4—Hg2—I3	150.11 (4)	C2i—S3—C1	95.7 (5)

Qx	nearest atom	distance	value
-Q1	Hg1	0.68	-3.29
Q1	Hg1	0.951	3.56
Q2	Hg2	0.994	1.67
Q3	Hg2	0.770	1.49
Q4	I3	0.797	1.07
Q5	Hg1	1.256	0.92
Q6	I3	0.688	0.92