(2,9-Dimethyl-4,7-diphenyl-1,10-phen­anthroline-κ2 N,N′)bis­(thio­cyanato-κS)mercury(II)

Robabeh Alizadeh

doi:10.1107/S1600536809023228

. 2009 Jun 24;65(Pt 7):m817–m818. doi: 10.1107/S1600536809023228

(2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline-κ² N,N′)bis(thiocyanato-κS)mercury(II)

Robabeh Alizadeh ^a,^*

PMCID: PMC2969232 PMID: 21582740

Abstract

In the molecule of the title compound, [Hg(NCS)₂(C₂₆H₂₀N₂)], the Hg^II atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from a chelating 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline ligand and by two S atoms from two thiocyanate anions. The ligand ring system is not planar. The dihedral angle between the phenyl rings is 53.20 (3)° . In the crystal structure, π–π contacts between phenanthroline rings [centroid–centroid distance = 3.981 (1) Å] may stabilize the structure.

Related literature

For related structures, see: Ahmadi et al. (2008 ▶); Alizadeh et al. (2009 ▶); Hughes et al. (1985 ▶); Kalateh et al. (2008 ▶); Khoshtarkib et al. (2009 ▶); Mahjoub & Morsali (2003 ▶); Morsali (2006 ▶); Morsali et al. (2003 ▶, 2004 ▶); Safari et al. (2009 ▶); Tadayon Pour et al. (2008 ▶); Xie et al. (2004 ▶); Yousefi et al. (2009 ▶); Yousefi, Rashidi Vahid et al. (2008 ▶); Yousefi, Tadayon Pour et al. (2008 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

[Hg(NCS)₂(C₂₆H₂₀N₂)]
M _r = 677.21
Orthorhombic,
a = 7.5907 (3) Å
b = 24.0254 (10) Å
c = 28.5284 (14) Å
V = 5202.7 (4) Å³
Z = 8
Mo Kα radiation
μ = 6.10 mm⁻¹
T = 298 K
0.40 × 0.05 × 0.04 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.711, T _max = 0.789
56419 measured reflections
7051 independent reflections
4018 reflections with I > 2σ(I)
R _int = 0.091

Refinement

R[F ² > 2σ(F ²)] = 0.093
wR(F ²) = 0.199
S = 1.21
7051 reflections
318 parameters
H-atom parameters constrained
Δρ_max = 2.55 e Å⁻³
Δρ_min = −1.43 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809023228/hk2711sup1.cif

e-65-0m817-sup1.cif^{(23.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023228/hk2711Isup2.hkl

e-65-0m817-Isup2.hkl^{(338.2KB, hkl)}

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

Table 1. Selected geometric parameters (Å, °).

Hg1—N2	2.309 (10)
Hg1—N1	2.320 (10)
Hg1—S2	2.443 (3)
Hg1—S1	2.456 (4)

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N2—Hg1—N1	71.7 (3)
N2—Hg1—S2	115.6 (2)
N1—Hg1—S2	118.6 (2)
N2—Hg1—S1	119.1 (2)
N1—Hg1—S1	114.7 (3)
S2—Hg1—S1	112.00 (12)

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Acknowledgments

We are grateful to the Damghan University of Basic Sciences for financial support.

supplementary crystallographic information

Comment

Recently, we reported the synthes and crystal structures of [Zn(phend)Cl₂], (II), (Alizadeh et al., 2009) and [Hg(2,9-dmphen)Br₂], (III), (Khoshtarkib et al., 2009) [where phend is phenanthridine and 2,9-dmphen is 2,9-dimethyl-1,10-phenanthroline]. There are several Hg^II complexes, with formula, [Hg(N—N)X₂], (X=Br, Cl, I and SCN), such as [Hg(TPA)Br₂], (IV), (Xie et al., 2004), [Hg(TPD)Br₂], (V), (Hughes et al., 1985), [Hg(NH(py)₂)Br₂], (VI), (Kalateh et al., 2008), [Hg(6-mbpy)Cl₂], (VII), (Ahmadi et al., 2008), [Hg(NH(py)₂)Cl₂], (IIX), (Yousefi, Allahgholi Ghasri et al., 2009), [Hg(4,4'-dmbpy)I₂], (IX), (Yousefi, Tadayon Pour et al., 2008), [Hg(5,5'-dmbpy)I₂], (X), (Tadayon Pour et al., 2008), [Hg(ph₂phen)I₂], (XI), (Yousefi, Rashidi Vahid et al., 2008), [Hg(SCN)₂(TBI)], (XII), (Morsali 2006), [Hg(dp4bt)(SCN)₂], (XIII), (Mahjoub & Morsali 2003), [Hg(da4bt)(SCN)₂], (XIV), (Morsali et al., 2003), [Hg(biq)(SCN)₂].C₆H₆, (XV), (Morsali et al., 2004) and [Hg(dm4bt)(SCN)₂], (XVI), (Safari et al., 2009) [where TPA is tris(2-pyridyl)amine, TPD is N,N,N',N'-Tetramethyl-o-phenylenediamine, NH(py)₂ is di-2-pyridylamine, 6-mbpy is 6-methyl-2,2'-bipyridine, 4,4'-dmbpy is 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dmbpy is 5,5'-dimethyl-2,2'-bipyridine, ph₂phen is 4,7-diphenyl-1,10-phenanthroline, TBI is 4,4',5,5'-tetramethyl-2,2'-bi-imidazole, dp4bt is 2,2'-diphenyl-4,4'-bithiazole, da4bt is 2,2'-diamino-4,4'-bithiazole, biq is 2,2'-biquinoline and dm4bt is 2,2'-dimethyl-4,4'-bithiazole] have been synthesized and characterized by single-crystal X-ray diffraction methods. We report herein the synthesis and crystal structure of the title compound (I).

In the molecule of the title compound (Fig 1), Hg^II atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline and two S atoms from two thiocyanate anions (Table 1). The bond lengths (Allen et al., 1987) and angles are within normal ranges, and are in accordance with the corresponding values in (XV). Rings A (N1/C2-C4/C11/C26), B (C11-C14/C25/C26) and C (N2/C14/C15/C22/C23/C25) are, of course, planar and the dihedral angles between them are A/B = 5.43 (3), A/C = 6.53 (3) and B/C = 4.07 (3) °. So, the phenanthroline ring system is not planar. The phenyl rings D (C5-C10) and E (C16-C21) are oriented at a dihedral angle of 53.20 (3)°.

In the crystal structure (Fig. 2), the π–π contact between the phenanthroline rings, Cg2—Cg2ⁱ [symmetry code: (i) 1/2 + x, 1/2 - y, z, where Cg2 is centroid of the ring B (C11-C14/C25/C26)] may stabilize the structure, with centroid-centroid distance of 3.981 (1) Å.

Experimental

For the preparation of the title compound, (I), a solution of 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (0.36 g, 1.10 mmol) in HCCl₃ (20 ml) was added to a solution of Hg(SCN)₂ (0.35 g, 1.10 mmol) in methanol (20 ml) and the resulting pale yellow solution was stirred for 20 min at room temperature, and then it was left to evaporate slowly at room temperature. After one week, colorless needle crystals of the title compound were isolated (yield; 0.53 g, 71.1%).