[1,5-Bis(4-fluoro­phen­yl)thio­carbazo­nato-κ2 N 5,S]phenyl­mercury(II) dichloro­methane hemisolvate

Karel G von Eschwege; Fabian Muller; Alfred Muller

doi:10.1107/S1600536811050331

. 2011 Nov 30;67(Pt 12):m1858–m1859. doi: 10.1107/S1600536811050331

[1,5-Bis(4-fluorophenyl)thiocarbazonato-κ² N ⁵,S]phenylmercury(II) dichloromethane hemisolvate

Karel G von Eschwege ^a,^*, Fabian Muller ^a, Alfred Muller ^b,^*

PMCID: PMC3238751 PMID: 22199628

Abstract

In the title compound, [Hg(C₆H₅)(C₁₃H₉F₂N₄S)]·0.5CH₂Cl₂, the Hg(C₆H₅) units are twisted out of the planes of the thiocarbazonate ligands by 61.49 (10) and 67.79 (11)° in the two complex molecules comprising the asymmetric unit. Important geometrical parameters include Hg—C = 2.079 (4) and 2.087 (4) Å, Hg—S = 2.3869 (10) and 2.3889 (11) Å, and C—Hg—S = 166.42 (12) and 168.09 (13)°. Weak intramolecular Hg—N bonding interactions of 2.589 (4) and 2.626 (4) Å are observed. In the crystal, C—H⋯Cl, C—H⋯F, C—H⋯N, C—H⋯π and π–π [centroid–centroid distances = 3.648 (3) and 3.641 (3) Å] interactions, create parallel planes along [101].

Related literature

For general background to thiocarbodiazonatomercury(II) complexes, see: Irving et al. (1949 ▶); Webb et al. (1950 ▶); von Eschwege et al. (2011 ▶). For synthetic procedures relating to the title compound, see: Mirkhalaf et al. (1998 ▶); von Eschwege et al. (2008 ▶). For details of the superimposed fitting of structures with Mercury, see: Weng et al. (2008a ▶,b ▶).

Experimental

Crystal data

[Hg(C₆H₅)(C₁₃H₉F₂N₄S)]·0.5CH₂Cl₂
M _r = 611.46
Monoclinic,
a = 31.996 (3) Å
b = 10.1889 (9) Å
c = 26.892 (2) Å
β = 116.818 (1)°
V = 7823.8 (12) Å³
Z = 16
Mo Kα radiation
μ = 8.14 mm⁻¹
T = 100 K
0.5 × 0.41 × 0.12 mm

Data collection

Bruker APEX DUO 4K CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T _min = 0.106, T _max = 0.441
94461 measured reflections
9726 independent reflections
8965 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.074
S = 1.21
9726 reflections
514 parameters
H-atom parameters constrained
Δρ_max = 3.10 e Å⁻³
Δρ_min = −2.47 e Å⁻³

Data collection: APEX2 (Bruker, 2011 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT and XPREP (Bruker, 2008 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg & Putz, 2005 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811050331/zq2140sup1.cif

e-67-m1858-sup1.cif^{(41.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811050331/zq2140Isup2.hkl

e-67-m1858-Isup2.hkl^{(466.2KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 and Cg2 are the centroids of the C2–C7 and C8–C13 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C28—H28⋯Cl1	0.95	2.77	3.598 (5)	146
C31—H31⋯F4ⁱ	0.95	2.53	3.413 (6)	155
C39—H39A⋯N2	0.99	2.62	3.558 (6)	158
C7—H7⋯Cg1ⁱⁱ	0.95	2.54	3.451 (5)	162
C12—H12⋯Cg2ⁱⁱⁱ	0.95	2.70	3.516 (6)	144
C26—H26⋯Cg2ⁱⁱ	0.95	2.69	3.500 (5)	144

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

Research funds of the University of Johannesburg and the National Research Foundation of South Africa are gratefully acknowledged.

supplementary crystallographic information

Comment

With the aim of investigating the influence of electron withdrawing groups on the photochromic (Irving et al., 1949; Webb et al., 1950) and redox reactions (von Eschwege et al., 2011) of dithizonatophenylmercury(II) complexes, a series of halogenated dithizones were synthesized and for the first time complexed with mercury. Deep orange-red needle crystals of the para-fluoro derivative, suitable for X-ray crystallography, were isolated from a dichloromethane solution overlaid with ethanol.

The asymmetric unit of the title compound contains two crystallographically independent mercury(II) molecules and one solvent molecule of dichloromethane (Fig. 1). Geometrical parameters of the two dithizonato complexes are fairly similar with Hg—C = 2.079 (4) / 2.087 (4) Å; Hg—S = 2.3869 (10) / 2.3889 (11) Å; and C—Hg—S = 166.42 (12)/ 168.09 (13)° for Hg1 and Hg2, respectively. The mercury coordination environments differ slightly and can be seen most prominently from the dihedral angles between the metal coordination plane vs. the plane formed by the dithizonato ligands (19.03 (8)° vs. 23.45 (8)° for Hg1 and Hg2, respectively). Differences between the two units are illustrated in Fig. 2 with a superimposed fit using Mercury (Weng et al., 2008a; Weng et al., 2008b). The root mean square deviation (RMSD) was calculated as 0.151 Å, and the maximum distance between two atoms = 0.333 Å.

Several interactions C—H···X (X = Cl, F, N), C—H···Cg (Table 1) and Cg···Cg (Table 2) stabilizes the crystal packing, creating parallel planes along the [101] direction (Fig. 3).

Experimental

Solvents (AR) purchased from Merck and reagents from Sigma-Aldrich were used without further purification. The para-fluoro derivative of dithizone, (p-FPhNHN)₂CS), was prepared according to the procedure reported by Mirkhalaf et al. (1998). The synthesis and crystallization of the title compound was done according to a procedure earlier reported by von Eschwege et al. (2008).