Chlorido[(E)-2-hydr­oxy-6-(isonicotinoyl­hydrazonometh­yl)phen­yl]mercury(II) monohydrate

Su-Zhen Bai; Xin-Hua Lou; Hong-Mei Li; Hui Shi

doi:10.1107/S1600536809023824

. 2009 Jun 27;65(Pt 7):m842–m843. doi: 10.1107/S1600536809023824

Chlorido[(E)-2-hydroxy-6-(isonicotinoylhydrazonomethyl)phenyl]mercury(II) monohydrate

Su-Zhen Bai ^a, Xin-Hua Lou ^b,^*, Hong-Mei Li ^c, Hui Shi ^a

PMCID: PMC2969284 PMID: 21582756

Abstract

The asymmetric unit of the title compound, [Hg(C₁₃H₁₀N₃O₂)Cl]·H₂O, contains two independent mercury(II) complexes with slightly different conformations, related via a pseudo-inversion centre, and two water molecules. The Hg^II atoms show a typical linear geometry to a C atom of the benzene ring and to a Cl atom. A benzene C and the azomethine N atom chelate the Hg^II atoms with weak intramolecular Hg⋯N bonding distances of 2.735 (3) and 2.739 (3) Å, respectively. The resulting five-membered metallacycles are nearly coplanar with the benzene rings [dihedral angles = 0.9 (1) and 0.7 (1)°], while the pyridine rings make dihedral angles with the benzene units of 58.17 (1) and 56.58 (1)°. In the crystal structure, the Hg^II complexes are linked by hydroxy donor and pyridine acceptor groups into chains along [010]. The water molecules connect the complexes through intermolecular O—H⋯O_carbonyl bonds in the a-axis direction, and the azomethine H atoms donate towards the water O atoms, forming a three-dimensional network of intermolecular O—H⋯N, O—H⋯O and N—H⋯O hydrogen bonds.

Related literature

For general background, see: Gruter et al. (1995 ▶); Soro et al. (2005 ▶); Xu et al. (2009b ▶). For related structures, see: Hao et al. (2007 ▶); Lin et al. (2002 ▶); For the synthesis of related cyclomercurated compounds, see: Xu et al. (2009a ▶).

Experimental

Crystal data

[Hg(C₁₃H₁₀N₃O₂)Cl]·H₂O
M _r = 494.30
Monoclinic,
a = 14.5932 (16) Å
b = 14.0111 (15) Å
c = 15.3711 (17) Å
β = 104.6850 (10)°
V = 3040.2 (6) Å³
Z = 8
Mo Kα radiation
μ = 10.31 mm⁻¹
T = 296 K
0.37 × 0.28 × 0.25 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.113, T _max = 0.179 (expected range = 0.048–0.076)
22798 measured reflections
5658 independent reflections
4683 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.021
wR(F ²) = 0.046
S = 1.05
5658 reflections
381 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.83 e Å⁻³

Data collection: SMART (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809023824/si2184sup1.cif

e-65-0m842-sup1.cif^{(24.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809023824/si2184Isup2.hkl

e-65-0m842-Isup2.hkl^{(277KB, hkl)}

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

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O6—H4W⋯O2ⁱ	0.83	2.15	2.898 (4)	150
O6—H3W⋯O3	0.83	2.30	3.023 (4)	146
O5—H2W⋯O1	0.83	2.17	2.963 (4)	159
O5—H1W⋯O4ⁱⁱ	0.84	2.06	2.876 (4)	166
N5—H5D⋯O6ⁱⁱⁱ	0.86	2.04	2.872 (4)	162
N2—H2D⋯O5^iv	0.86	2.06	2.890 (4)	161
O3—H3⋯N6^v	0.82	1.92	2.737 (4)	171
O1—H1⋯N3^vi	0.82	1.93	2.733 (4)	167

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

Acknowledgments

This work was supported by the High-Level Personnel to Start Research Fund of Pingdingshan University (No. 2006044).

supplementary crystallographic information

Comment

Cyclometallated compounds have attracted much research interest owing to theirs utility in synthesis, catalysis and materials (Gruter et al., 1995; Xu et al., 2009b). Among them, cyclomercurated compounds are easy to prepare through a C—H activation process and are stable but reasonably reactive. Although numerous cyclomercurated compounds have been widely investigated, and many examples have been reported(Soro et al., 2005; Hao et al., 2007), only a few cyclometallated Schiff bases containing heterocyclic ring are known(Lin et al., 2002).

The asymmetric unit of the title compound (Fig.1) contains two independent mercury(II) complexes with slightly different conformations, related via a pseudo-inversion centre (1/2a, 3/4b, 1/4c), and two water molecules. The Hg^II atoms show a typical linear coordination geometry with a carbon atom of the benzene ring and the chloride atom in trans position. A benzene carbon and the azomethine nitrogen atom chelate the mercury(II) atoms with weak intramolecular Hg···N bonding distances of 2.735 (3)Å and 2.739 (3) Å. which are shorter than those of the related Hg^II complex (Hao et al., (2007); Lin et al., (2002); Xu et al., (2009a). The C—Hg and Hg—Cl bond distances are within normal ranges. The C1—Hg1—Cl1 and C14—Hg2—Cl2 angles are 173.85 (10)° and 174.67 (10)°, slightly smaller than the ideal value of 180° in organic derivatives of mercury. The resulting five-membered metallacycles are nearly coplanar with the benzene ring, while the pyridine are not coplanar with the benzene. In the crystal structure, intermolecular O—H···O, N—H···O and O—H···N hydrogen bonds (Table 1) link the independent Hg^II complexes and the water molecules into a three-dimensional network.

Experimental

Chlorido(2-formyl-6-hydroxybenzaldehyde-kC¹)mercury(II) was synthesized according to the reported procedure (Xu et al., 2009a). The title compound was prepared from the above compound with isonicotinoylhydrazine and recrystallized from ethanol solution at room temperature to give the desired product as colourless crystals suitable for single-crystal X-ray diffraction.