Iodido{4-phenyl-1-[1-(1,3-thia­zol-2-yl-κN)ethyl­idene]thio­semicarbazidato-κ2N′,S}{4-phenyl-1-[1-(1,3-thia­zol-2-yl)ethyl­idene]thio­semicarbazide-κS}mercury(II)

Dasary, S.S.R.; Arumugam, S.R.; Yu, H.; Venkatraman, R.; Fronczek, F.R.

doi:10.1107/S160053681101974X

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 6| June 2011| Pages m816-m817

doi:10.1107/S160053681101974X

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Iodido{4-phenyl-1-[1-(1,3-thiazol-2-yl-κN)ethylidene]thiosemicarbazidato-κ²N′,S}{4-phenyl-1-[1-(1,3-thiazol-2-yl)ethylidene]thiosemicarbazide-κS}mercury(II)

Samuel S. R. Dasary,^a Sri Ranjini Arumugam,^a Hongtao Yu,^a Ramaiyer Venkatraman ^a and Frank R. Fronczek ^b ^*

^aDepartment of Chemistry and Biochemistry, Jackson State University, Jackson, MS 39217, USA, and ^bDepartment of Chemistry, Louisiana State University, Baton Rouge, LA 70803, USA
^*Correspondence e-mail: ffroncz@lsu.edu

(Received 23 April 2011; accepted 24 May 2011; online 28 May 2011)

In the title compound, [Hg(C₁₂H₁₁N₄S₂)I(C₁₂H₁₂N₄S₂)], the Hg atom is in a distorted square-pyramidal coordination, defined by the iodide ligand, by the S atom of the neutral ligand in the apical position, and by the N atom of the thiazole ring, the thioureido N and the S atom of the deprotonated ligand. The deprotonated ligand intramolecularly hydrogen bonds to the thiazole ring N atom, while the deprotonated ligand forms an intermolecular hydrogen bond to the thiolate S atom. The deprotonation of the tridentate ligand and its coordination to Hg via the S atom strikingly affects the C—S bond lengths. In the free ligand, the C—S bond distance is 1.685 (7) Å, whereas it is 1.749 (7) Å in the deprotonated ligand. Similarly, the Hg—S bond distance is slightly longer to the neutral ligand [2.6682 (18) Å] than to the deprotonated ligand [2.5202 (19) Å]. The Hg—I distance is 2.7505 (8) Å.

Related literature

For general background to thiosemicarbazones and their Hg complexes, see: Akinchan et al. (2002 ); Ali & Livingstone (1974 ); Bermejo et al. (1999 , 2003 ); Lobana et al. (1998 ); Venkatraman et al. (2009 ); Blanz & French (1968 ); Campbell (1975 ); Casas et al. (2000 ); Grecu & Neamtu (1967 ); Pellerito & Negy (2002 ); Raper (1985 ).

Experimental

Crystal data

[Hg(C₁₂H₁₁N₄S₂)I(C₁₂H₁₂N₄S₂)]
M_r = 879.23
Triclinic, $[P \overline 1]$
a = 8.694 (2) Å
b = 10.119 (2) Å
c = 16.801 (4) Å
α = 76.670 (13)°
β = 79.448 (12)°
γ = 77.190 (13)°
V = 1388.8 (5) Å³
Z = 2
Mo Kα radiation
μ = 6.99 mm⁻¹
T = 90 K
0.10 × 0.10 × 0.03 mm

Data collection

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997 ) T_min = 0.542, T_max = 0.818
21861 measured reflections
5837 independent reflections
4289 reflections with I > 2σ(I)
R_int = 0.059

Refinement

R[F² > 2σ(F²)] = 0.042
wR(F²) = 0.085
S = 1.02
5837 reflections
346 parameters
H-atom parameters constrained
Δρ_max = 1.36 e Å⁻³
Δρ_min = −1.27 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N7—H7N⋯N5	0.88	1.97	2.667 (8)	135
N4—H4N⋯S2ⁱ	0.88	2.69	3.553 (6)	167
Symmetry code: (i) -x, -y+2, -z+1.

Data collection: COLLECT (Nonius, 2000 ); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997) and SCALEPACK; 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 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681101974X/vm2089sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053681101974X/vm2089Isup2.hkl

checkCIF report

Comment top

Studies on thiosemicarbazones and their metal complexes has remained a fertile field of research for more than three decades due to their significant impacts in biology and chemistry (Ali & Livingstone, 1974; Campbell, 1975; Pellerito & Negy, 2002). Thiosemicarbazones are known to coordinate to many metals, potentially as tridentate ligands. The ligation can occur with the metals as a neutral molecule or, after deprotonation, as an anionic ligand (Campbell, 1975; Raper, 1985; Casas et al., 2000). Further, the metal-chelating ability is attributed to the thione-thiol tautomerism exhibited by these molecules. Some of the metal complexes are found to exhibit enhanced biological activity compared to their basic ligand (Blanz & French, 1968). Among the metals studied with thiosemicarbazones, mercury and organomercury compounds are scarce (Grecu & Neamtu, 1967; Lobana et al.,1998; Bermejo et al., 1999; Akinchan et al., 2002; Bermejo et al., 2003). Removal and remediation of many mercury species from environmental samples are very important. We report here the synthesis and structure of a mercury(II) iodide complex of the phenyl derivative of 2-acetylthiazole-3-thiosemicarbazone. The title complex is a result of interaction between two neutral ligand molecules and mercury(II) iodide in methanol. In this complex, Hg(II) is chelated by two 2-acetylthiazole-3-phenylthiosemicarbazone ligands, forming a distorted square pyramidal geometry (Fig 1). One of the two ligands is deprotonated at N3, and tridentate through its N, N, S atoms. Along with the iodide atom, it forms the square planar base. The other ligand is neutral and apical to the Hg atom, binding through its S atom. The proton NMR also provides the evidence of ligand deprotonation during metal chelation. The sharp resonance signal due to N—NH proton at 11.12 p.p.m. disappears in the spectrum of the complex. The N4 signal (at ~8.64 p.p.m.) in the ligand undergoes a downfield shift that is marked in the mercury (II) complexes, indicating coordination via the S atom. The protonated and deprotonated ligands have different conformations, differing primarily by the N–N–C–N torsion angle, which is antiperiplanar in the deprotonated ligand (torsion angle N2—N3—C6—N4 179.6 (5)°) and synperiplanar in the neutral ligand (torsion angle N6—N7—C18—N8 9.3 (9)°). Hydrogen bonding details are given in Table 1.

Related literature top

For general background to thiosemicarbazones and their Hg complexes, see: Akinchan et al. (2002); Ali et al. (1974); Bermejo et al. (1999, 2003); Lobana et al. (1998); Venkatraman et al. (2009); Blanz & French (1968); Campbell (1975); Casas et al. (2000); Grecu & Neamtu (1967); Pellerito & Negy (2002); Raper (1985).

Experimental top

To a solution of 2-acetyl thiazole thiosemicarbazone (Venkatraman et al. 2009) (1.38 g, 5 mmol) in warm methanol (50 ml) was added an equimolar methanol solution (50 ml) of mercury(II) iodide (1.36 g. 5 mmol). The mixture was stirred for about 24 h, after which time the yellow solid obtained was filtered and vacuum dried (yield ~75%). Crystals suitable for diffraction studies were obtained from the mother liquor at room temperature after a week.

Computing details top

Data collection: COLLECT (Nonius, 2000); cell refinement: SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO and SCALEPACK (Otwinowski & Minor, 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); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level.

Iodido{4-phenyl-1-[1-(1,3-thiazol-2-yl- κN)ethylidene]thiosemicarbazidato-κ²N',S}{4- phenyl-1-[1-(1,3-thiazol-2-yl)ethylidene]thiosemicarbazide- κS}mercury(II) top

Crystal data top

[Hg(C₁₂H₁₁N₄S₂)I(C₁₂H₁₂N₄S₂)]	Z = 2
M_r = 879.23	F(000) = 840
Triclinic, P1	D_x = 2.103 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.694 (2) Å	Cell parameters from 5532 reflections
b = 10.119 (2) Å	θ = 2.5–26.7°
c = 16.801 (4) Å	µ = 6.99 mm⁻¹
α = 76.670 (13)°	T = 90 K
β = 79.448 (12)°	Parallelepiped, yellow
γ = 77.190 (13)°	0.10 × 0.10 × 0.03 mm
V = 1388.8 (5) Å³

Data collection top

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler	5837 independent reflections
Radiation source: fine-focus sealed tube	4289 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.059
ω and ϕ scans	θ_max = 26.7°, θ_min = 2.8°
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	h = −10→10
T_min = 0.542, T_max = 0.818	k = −11→12
21861 measured reflections	l = −21→21

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.042	H-atom parameters constrained
wR(F²) = 0.085	w = 1/[σ²(F_o²) + (0.0336P)²] where P = (F_o² + 2F_c²)/3
S = 1.02	(Δ/σ)_max = 0.001
5837 reflections	Δρ_max = 1.36 e Å⁻³
346 parameters	Δρ_min = −1.27 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00093 (17)

Crystal data top

[Hg(C₁₂H₁₁N₄S₂)I(C₁₂H₁₂N₄S₂)]	γ = 77.190 (13)°
M_r = 879.23	V = 1388.8 (5) Å³
Triclinic, P1	Z = 2
a = 8.694 (2) Å	Mo Kα radiation
b = 10.119 (2) Å	µ = 6.99 mm⁻¹
c = 16.801 (4) Å	T = 90 K
α = 76.670 (13)°	0.10 × 0.10 × 0.03 mm
β = 79.448 (12)°

Data collection top

Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler	5837 independent reflections
Absorption correction: multi-scan (SCALEPACK; Otwinowski & Minor, 1997)	4289 reflections with I > 2σ(I)
T_min = 0.542, T_max = 0.818	R_int = 0.059
21861 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.042	0 restraints
wR(F²) = 0.085	H-atom parameters constrained
S = 1.02	Δρ_max = 1.36 e Å⁻³
5837 reflections	Δρ_min = −1.27 e Å⁻³
346 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Hg1	0.31186 (3)	0.89942 (3)	0.265558 (18)	0.01642 (10)
I1	0.21508 (5)	1.07878 (4)	0.12625 (3)	0.01901 (13)
S1	0.8957 (2)	0.80421 (19)	0.20242 (13)	0.0233 (4)
S2	0.1598 (2)	0.96404 (18)	0.39821 (11)	0.0190 (4)
S3	0.9843 (2)	0.36980 (18)	0.41473 (12)	0.0203 (4)
S4	0.2697 (2)	0.64537 (17)	0.26747 (11)	0.0160 (4)
N1	0.5975 (7)	0.8585 (6)	0.1973 (4)	0.0172 (13)
N2	0.5053 (6)	0.8499 (5)	0.3621 (4)	0.0140 (13)
N3	0.4585 (6)	0.8448 (6)	0.4445 (4)	0.0167 (13)
N4	0.2463 (7)	0.8923 (5)	0.5448 (4)	0.0167 (13)
H4N	0.1422	0.9187	0.5536	0.020*
N5	0.6878 (7)	0.4722 (5)	0.4101 (4)	0.0165 (13)
N6	0.7246 (6)	0.4946 (5)	0.2273 (4)	0.0148 (13)
N7	0.5745 (6)	0.5393 (5)	0.2660 (4)	0.0153 (13)
H7N	0.5599	0.5437	0.3186	0.018*
N8	0.4802 (7)	0.5470 (5)	0.1473 (4)	0.0193 (14)
H8N	0.5761	0.5022	0.1321	0.023*
C1	0.6692 (9)	0.8629 (7)	0.1192 (5)	0.0246 (18)
H1	0.6108	0.8833	0.0739	0.029*
C2	0.8316 (9)	0.8360 (7)	0.1094 (5)	0.0263 (19)
H2	0.8988	0.8352	0.0580	0.032*
C3	0.6998 (8)	0.8271 (6)	0.2493 (5)	0.0176 (16)
C4	0.6563 (8)	0.8224 (7)	0.3384 (4)	0.0162 (16)
C5	0.7824 (8)	0.7881 (7)	0.3942 (5)	0.0220 (17)
H5A	0.7641	0.8587	0.4280	0.033*
H5B	0.8875	0.7858	0.3608	0.033*
H5C	0.7778	0.6975	0.4303	0.033*
C6	0.3053 (9)	0.8937 (7)	0.4635 (4)	0.0174 (16)
C7	0.3180 (8)	0.8573 (6)	0.6171 (4)	0.0159 (16)
C8	0.4837 (8)	0.8114 (7)	0.6195 (5)	0.0199 (17)
H8	0.5544	0.7976	0.5706	0.024*
C9	0.5407 (9)	0.7870 (7)	0.6942 (5)	0.0216 (17)
H9	0.6518	0.7563	0.6957	0.026*
C10	0.4416 (9)	0.8057 (7)	0.7667 (5)	0.0222 (17)
H10	0.4838	0.7899	0.8171	0.027*
C11	0.2783 (9)	0.8484 (7)	0.7643 (5)	0.0194 (16)
H11	0.2079	0.8606	0.8135	0.023*
C12	0.2183 (9)	0.8730 (7)	0.6898 (4)	0.0198 (17)
H12	0.1068	0.9012	0.6889	0.024*
C13	0.7128 (8)	0.4433 (6)	0.4910 (4)	0.0153 (15)
H13	0.6288	0.4601	0.5345	0.018*
C14	0.8635 (8)	0.3898 (7)	0.5051 (5)	0.0206 (17)
H14	0.8980	0.3663	0.5579	0.025*
C15	0.8228 (8)	0.4387 (6)	0.3616 (4)	0.0159 (16)
C16	0.8390 (8)	0.4512 (6)	0.2728 (5)	0.0165 (16)
C17	1.0026 (8)	0.4099 (7)	0.2277 (5)	0.0194 (17)
H17A	0.9990	0.4341	0.1680	0.029*
H17B	1.0388	0.3099	0.2441	0.029*
H17C	1.0766	0.4587	0.2415	0.029*
C18	0.4504 (8)	0.5761 (7)	0.2232 (4)	0.0164 (16)
C19	0.3674 (8)	0.5833 (7)	0.0882 (4)	0.0151 (15)
C20	0.3171 (8)	0.7201 (7)	0.0526 (5)	0.0209 (17)
H20	0.3519	0.7919	0.0682	0.025*
C21	0.2147 (8)	0.7508 (8)	−0.0067 (4)	0.0213 (17)
H21	0.1763	0.8444	−0.0305	0.026*
C22	0.1693 (8)	0.6466 (7)	−0.0307 (4)	0.0195 (17)
H22	0.1029	0.6680	−0.0728	0.023*
C23	0.2196 (8)	0.5104 (7)	0.0058 (4)	0.0176 (16)
H23	0.1845	0.4386	−0.0096	0.021*
C24	0.3209 (8)	0.4785 (7)	0.0647 (4)	0.0151 (15)
H24	0.3581	0.3848	0.0889	0.018*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.01578 (16)	0.01912 (16)	0.01491 (17)	−0.00140 (11)	−0.00418 (11)	−0.00464 (11)
I1	0.0239 (3)	0.0162 (2)	0.0163 (3)	−0.0001 (2)	−0.0067 (2)	−0.0026 (2)
S1	0.0140 (10)	0.0241 (10)	0.0307 (12)	−0.0032 (8)	−0.0002 (8)	−0.0058 (9)
S2	0.0186 (10)	0.0227 (9)	0.0150 (10)	0.0023 (8)	−0.0049 (8)	−0.0061 (8)
S3	0.0177 (10)	0.0235 (9)	0.0218 (11)	−0.0023 (8)	−0.0075 (8)	−0.0061 (8)
S4	0.0152 (9)	0.0190 (9)	0.0153 (10)	−0.0037 (8)	−0.0029 (7)	−0.0049 (7)
N1	0.020 (3)	0.019 (3)	0.014 (4)	−0.003 (3)	−0.001 (3)	−0.006 (3)
N2	0.015 (3)	0.013 (3)	0.015 (3)	−0.002 (2)	−0.001 (3)	−0.007 (2)
N3	0.013 (3)	0.020 (3)	0.015 (3)	−0.001 (3)	−0.001 (3)	−0.003 (3)
N4	0.016 (3)	0.020 (3)	0.013 (3)	0.000 (3)	−0.002 (3)	−0.003 (3)
N5	0.020 (3)	0.012 (3)	0.018 (4)	−0.004 (3)	0.000 (3)	−0.003 (3)
N6	0.012 (3)	0.011 (3)	0.021 (4)	−0.004 (2)	0.005 (3)	−0.007 (3)
N7	0.019 (3)	0.020 (3)	0.007 (3)	−0.003 (3)	−0.004 (3)	−0.003 (2)
N8	0.020 (3)	0.015 (3)	0.024 (4)	0.003 (3)	−0.008 (3)	−0.009 (3)
C1	0.029 (5)	0.024 (4)	0.021 (5)	−0.007 (4)	−0.007 (4)	−0.002 (3)
C2	0.026 (4)	0.023 (4)	0.028 (5)	−0.003 (4)	−0.005 (4)	−0.002 (4)
C3	0.020 (4)	0.009 (3)	0.020 (4)	−0.001 (3)	0.004 (3)	−0.001 (3)
C4	0.016 (4)	0.015 (3)	0.020 (4)	−0.002 (3)	−0.010 (3)	−0.002 (3)
C5	0.024 (4)	0.020 (4)	0.023 (4)	−0.003 (3)	−0.011 (3)	−0.002 (3)
C6	0.028 (4)	0.014 (3)	0.015 (4)	−0.007 (3)	−0.005 (3)	−0.008 (3)
C7	0.024 (4)	0.011 (3)	0.014 (4)	−0.004 (3)	−0.007 (3)	−0.003 (3)
C8	0.016 (4)	0.018 (4)	0.027 (5)	−0.001 (3)	−0.007 (3)	−0.006 (3)
C9	0.019 (4)	0.019 (4)	0.027 (5)	0.002 (3)	−0.008 (3)	−0.005 (3)
C10	0.041 (5)	0.016 (4)	0.013 (4)	−0.014 (4)	−0.012 (4)	0.006 (3)
C11	0.030 (4)	0.015 (3)	0.017 (4)	−0.010 (3)	−0.006 (3)	−0.004 (3)
C12	0.027 (4)	0.022 (4)	0.014 (4)	−0.005 (3)	−0.011 (3)	−0.002 (3)
C13	0.019 (4)	0.013 (3)	0.012 (4)	−0.005 (3)	0.000 (3)	−0.001 (3)
C14	0.023 (4)	0.019 (4)	0.020 (4)	−0.005 (3)	−0.004 (3)	−0.001 (3)
C15	0.021 (4)	0.010 (3)	0.020 (4)	−0.004 (3)	−0.008 (3)	−0.003 (3)
C16	0.021 (4)	0.010 (3)	0.023 (4)	−0.003 (3)	−0.006 (3)	−0.008 (3)
C17	0.018 (4)	0.017 (4)	0.025 (5)	−0.004 (3)	−0.004 (3)	−0.006 (3)
C18	0.025 (4)	0.011 (3)	0.016 (4)	−0.007 (3)	−0.010 (3)	−0.001 (3)
C19	0.014 (4)	0.020 (4)	0.007 (4)	0.001 (3)	−0.001 (3)	0.000 (3)
C20	0.023 (4)	0.019 (4)	0.025 (5)	0.000 (3)	−0.006 (3)	−0.014 (3)
C21	0.022 (4)	0.029 (4)	0.011 (4)	0.000 (3)	−0.007 (3)	−0.002 (3)
C22	0.022 (4)	0.023 (4)	0.015 (4)	−0.006 (3)	−0.005 (3)	−0.003 (3)
C23	0.015 (4)	0.025 (4)	0.020 (4)	−0.010 (3)	−0.005 (3)	−0.011 (3)
C24	0.014 (4)	0.012 (3)	0.015 (4)	−0.002 (3)	−0.001 (3)	0.003 (3)

Geometric parameters (Å, º) top

Hg1—N2	2.441 (6)	C5—H5A	0.9800
Hg1—S2	2.5202 (19)	C5—H5B	0.9800
Hg1—N1	2.525 (6)	C5—H5C	0.9800
Hg1—S4	2.6682 (18)	C7—C12	1.382 (10)
Hg1—I1	2.7505 (8)	C7—C8	1.417 (9)
S1—C2	1.693 (8)	C8—C9	1.383 (10)
S1—C3	1.730 (7)	C8—H8	0.9500
S2—C6	1.749 (7)	C9—C10	1.383 (10)
S3—C14	1.706 (8)	C9—H9	0.9500
S3—C15	1.730 (7)	C10—C11	1.394 (10)
S4—C18	1.685 (7)	C10—H10	0.9500
N1—C3	1.299 (9)	C11—C12	1.392 (9)
N1—C1	1.341 (9)	C11—H11	0.9500
N2—C4	1.287 (8)	C12—H12	0.9500
N2—N3	1.361 (8)	C13—C14	1.344 (9)
N3—C6	1.321 (9)	C13—H13	0.9500
N4—C6	1.366 (9)	C14—H14	0.9500
N4—C7	1.403 (8)	C15—C16	1.450 (10)
N4—H4N	0.8800	C16—C17	1.503 (9)
N5—C15	1.326 (9)	C17—H17A	0.9800
N5—C13	1.370 (9)	C17—H17B	0.9800
N6—C16	1.304 (8)	C17—H17C	0.9800
N6—N7	1.376 (7)	C19—C24	1.372 (9)
N7—C18	1.342 (8)	C19—C20	1.382 (9)
N7—H7N	0.8800	C20—C21	1.393 (9)
N8—C18	1.340 (9)	C20—H20	0.9500
N8—C19	1.454 (8)	C21—C22	1.367 (10)
N8—H8N	0.8800	C21—H21	0.9500
C1—C2	1.364 (10)	C22—C23	1.382 (9)
C1—H1	0.9500	C22—H22	0.9500
C2—H2	0.9500	C23—C24	1.380 (9)
C3—C4	1.468 (10)	C23—H23	0.9500
C4—C5	1.503 (9)	C24—H24	0.9500

N2—Hg1—S2	73.61 (13)	N4—C7—C8	124.5 (6)
N2—Hg1—N1	66.52 (19)	C9—C8—C7	118.9 (7)
S2—Hg1—N1	137.91 (14)	C9—C8—H8	120.5
N2—Hg1—S4	101.14 (13)	C7—C8—H8	120.5
S2—Hg1—S4	106.40 (6)	C8—C9—C10	122.3 (7)
N1—Hg1—S4	94.22 (13)	C8—C9—H9	118.8
N2—Hg1—I1	143.13 (13)	C10—C9—H9	118.8
S2—Hg1—I1	113.54 (4)	C9—C10—C11	118.6 (7)
N1—Hg1—I1	91.86 (13)	C9—C10—H10	120.7
S4—Hg1—I1	110.31 (4)	C11—C10—H10	120.7
C2—S1—C3	89.6 (4)	C12—C11—C10	120.1 (7)
C6—S2—Hg1	99.8 (2)	C12—C11—H11	120.0
C14—S3—C15	89.6 (4)	C10—C11—H11	120.0
C18—S4—Hg1	101.0 (2)	C7—C12—C11	121.3 (7)
C3—N1—C1	112.0 (6)	C7—C12—H12	119.4
C3—N1—Hg1	113.2 (5)	C11—C12—H12	119.4
C1—N1—Hg1	134.8 (5)	C14—C13—N5	115.8 (6)
C4—N2—N3	116.5 (6)	C14—C13—H13	122.1
C4—N2—Hg1	121.9 (5)	N5—C13—H13	122.1
N3—N2—Hg1	121.5 (4)	C13—C14—S3	110.5 (6)
C6—N3—N2	113.7 (6)	C13—C14—H14	124.7
C6—N4—C7	133.0 (6)	S3—C14—H14	124.7
C6—N4—H4N	113.5	N5—C15—C16	125.3 (6)
C7—N4—H4N	113.5	N5—C15—S3	113.5 (5)
C15—N5—C13	110.6 (6)	C16—C15—S3	121.1 (5)
C16—N6—N7	117.3 (6)	N6—C16—C15	126.4 (6)
C18—N7—N6	119.7 (6)	N6—C16—C17	115.7 (6)
C18—N7—H7N	120.1	C15—C16—C17	117.9 (6)
N6—N7—H7N	120.1	C16—C17—H17A	109.5
C18—N8—C19	125.5 (6)	C16—C17—H17B	109.5
C18—N8—H8N	117.2	H17A—C17—H17B	109.5
C19—N8—H8N	117.2	C16—C17—H17C	109.5
N1—C1—C2	115.3 (7)	H17A—C17—H17C	109.5
N1—C1—H1	122.3	H17B—C17—H17C	109.5
C2—C1—H1	122.3	N8—C18—N7	115.6 (6)
C1—C2—S1	109.8 (6)	N8—C18—S4	124.3 (5)
C1—C2—H2	125.1	N7—C18—S4	120.0 (5)
S1—C2—H2	125.1	C24—C19—C20	121.1 (6)
N1—C3—C4	124.1 (6)	C24—C19—N8	118.4 (6)
N1—C3—S1	113.3 (5)	C20—C19—N8	120.3 (6)
C4—C3—S1	122.5 (6)	C19—C20—C21	118.8 (7)
N2—C4—C3	114.2 (6)	C19—C20—H20	120.6
N2—C4—C5	125.1 (7)	C21—C20—H20	120.6
C3—C4—C5	120.7 (6)	C22—C21—C20	120.2 (7)
C4—C5—H5A	109.5	C22—C21—H21	119.9
C4—C5—H5B	109.5	C20—C21—H21	119.9
H5A—C5—H5B	109.5	C21—C22—C23	120.3 (7)
C4—C5—H5C	109.5	C21—C22—H22	119.8
H5A—C5—H5C	109.5	C23—C22—H22	119.8
H5B—C5—H5C	109.5	C24—C23—C22	120.1 (6)
N3—C6—N4	118.2 (6)	C24—C23—H23	120.0
N3—C6—S2	129.1 (6)	C22—C23—H23	120.0
N4—C6—S2	112.7 (5)	C19—C24—C23	119.4 (6)
C12—C7—N4	116.6 (6)	C19—C24—H24	120.3
C12—C7—C8	118.9 (7)	C23—C24—H24	120.3

N2—Hg1—S2—C6	−10.2 (3)	N2—N3—C6—N4	179.6 (5)
N1—Hg1—S2—C6	−29.3 (3)	N2—N3—C6—S2	−0.8 (9)
S4—Hg1—S2—C6	86.9 (2)	C7—N4—C6—N3	5.6 (11)
I1—Hg1—S2—C6	−151.6 (2)	C7—N4—C6—S2	−174.0 (6)
N2—Hg1—S4—C18	−66.7 (3)	Hg1—S2—C6—N3	11.2 (7)
S2—Hg1—S4—C18	−142.7 (3)	Hg1—S2—C6—N4	−169.2 (4)
N1—Hg1—S4—C18	0.1 (3)	C6—N4—C7—C12	178.0 (7)
I1—Hg1—S4—C18	93.7 (3)	C6—N4—C7—C8	−0.1 (11)
N2—Hg1—N1—C3	2.4 (4)	C12—C7—C8—C9	−1.5 (10)
S2—Hg1—N1—C3	22.4 (6)	N4—C7—C8—C9	176.6 (6)
S4—Hg1—N1—C3	−97.9 (5)	C7—C8—C9—C10	0.0 (10)
I1—Hg1—N1—C3	151.6 (4)	C8—C9—C10—C11	1.2 (10)
N2—Hg1—N1—C1	−176.8 (7)	C9—C10—C11—C12	−0.9 (10)
S2—Hg1—N1—C1	−156.8 (5)	N4—C7—C12—C11	−176.5 (6)
S4—Hg1—N1—C1	82.9 (6)	C8—C7—C12—C11	1.8 (10)
I1—Hg1—N1—C1	−27.6 (6)	C10—C11—C12—C7	−0.6 (10)
S2—Hg1—N2—C4	−168.3 (5)	C15—N5—C13—C14	0.5 (8)
N1—Hg1—N2—C4	−2.1 (5)	N5—C13—C14—S3	−1.0 (8)
S4—Hg1—N2—C4	87.7 (5)	C15—S3—C14—C13	1.0 (5)
I1—Hg1—N2—C4	−60.8 (6)	C13—N5—C15—C16	177.9 (6)
S2—Hg1—N2—N3	14.3 (4)	C13—N5—C15—S3	0.3 (7)
N1—Hg1—N2—N3	−179.5 (5)	C14—S3—C15—N5	−0.7 (5)
S4—Hg1—N2—N3	−89.7 (4)	C14—S3—C15—C16	−178.4 (6)
I1—Hg1—N2—N3	121.8 (4)	N7—N6—C16—C15	3.3 (10)
C4—N2—N3—C6	170.4 (6)	N7—N6—C16—C17	−177.1 (5)
Hg1—N2—N3—C6	−12.1 (7)	N5—C15—C16—N6	−1.2 (11)
C16—N6—N7—C18	−175.4 (6)	S3—C15—C16—N6	176.2 (5)
C3—N1—C1—C2	−0.8 (9)	N5—C15—C16—C17	179.2 (6)
Hg1—N1—C1—C2	178.4 (5)	S3—C15—C16—C17	−3.4 (8)
N1—C1—C2—S1	−0.1 (8)	C19—N8—C18—N7	−176.6 (6)
C3—S1—C2—C1	0.6 (6)	C19—N8—C18—S4	6.9 (10)
C1—N1—C3—C4	176.5 (6)	N6—N7—C18—N8	9.3 (9)
Hg1—N1—C3—C4	−2.9 (8)	N6—N7—C18—S4	−174.1 (4)
C1—N1—C3—S1	1.2 (7)	Hg1—S4—C18—N8	−109.2 (6)
Hg1—N1—C3—S1	−178.1 (3)	Hg1—S4—C18—N7	74.5 (5)
C2—S1—C3—N1	−1.1 (5)	C18—N8—C19—C24	−116.1 (7)
C2—S1—C3—C4	−176.4 (6)	C18—N8—C19—C20	68.1 (9)
N3—N2—C4—C3	179.0 (5)	C24—C19—C20—C21	1.5 (11)
Hg1—N2—C4—C3	1.5 (8)	N8—C19—C20—C21	177.1 (6)
N3—N2—C4—C5	−1.2 (9)	C19—C20—C21—C22	−2.1 (11)
Hg1—N2—C4—C5	−178.7 (5)	C20—C21—C22—C23	2.5 (11)
N1—C3—C4—N2	1.2 (10)	C21—C22—C23—C24	−2.4 (11)
S1—C3—C4—N2	175.9 (5)	C20—C19—C24—C23	−1.3 (10)
N1—C3—C4—C5	−178.7 (6)	N8—C19—C24—C23	−177.0 (6)
S1—C3—C4—C5	−3.9 (9)	C22—C23—C24—C19	1.8 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7N···N5	0.88	1.97	2.667 (8)	135
N4—H4N···S2ⁱ	0.88	2.69	3.553 (6)	167

Symmetry code: (i) −x, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	[Hg(C₁₂H₁₁N₄S₂)I(C₁₂H₁₂N₄S₂)]
M_r	879.23
Crystal system, space group	Triclinic, P1
Temperature (K)	90
a, b, c (Å)	8.694 (2), 10.119 (2), 16.801 (4)
α, β, γ (°)	76.670 (13), 79.448 (12), 77.190 (13)
V (Å³)	1388.8 (5)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	6.99
Crystal size (mm)	0.10 × 0.10 × 0.03

Data collection
Diffractometer	Nonius KappaCCD diffractometer with an Oxford Cryosystems Cryostream cooler
Absorption correction	Multi-scan (SCALEPACK; Otwinowski & Minor, 1997)
T_min, T_max	0.542, 0.818
No. of measured, independent and observed [I > 2σ(I)] reflections	21861, 5837, 4289
R_int	0.059
(sin θ/λ)_max (Å⁻¹)	0.632

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.042, 0.085, 1.02
No. of reflections	5837
No. of parameters	346
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.36, −1.27

Computer programs: COLLECT (Nonius, 2000), DENZO and SCALEPACK (Otwinowski & Minor, 1997), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N7—H7N···N5	0.88	1.97	2.667 (8)	135
N4—H4N···S2ⁱ	0.88	2.69	3.553 (6)	167

Symmetry code: (i) −x, −y+2, −z+1.

Acknowledgements

Purchase of the diffractometer was made possible by grant No. LEQSF (1999–2000)-ENH-TR-13, administered by the Louisiana Board of Regents. RV acknowledges the JSU Department of Chemistry and Biochemistry for the supplies and utilization of lab facilities.

References

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