Poly[di-μ-chlorido-μ-(1,2,3,9-tetra­hydro­pyrrolo­[2,1-b]quinazolin-9-one-κ2 N:O)-mercury(II)]

Kambarali K Turgunov; Yutian Wang; Ulli Englert; Khusnutdin M Shakhidoyatov

doi:10.1107/S1600536811022471

. 2011 Jun 18;67(Pt 7):m953–m954. doi: 10.1107/S1600536811022471

Poly[di-μ-chlorido-μ-(1,2,3,9-tetrahydropyrrolo[2,1-b]quinazolin-9-one-κ² N:O)-mercury(II)]

Kambarali K Turgunov ^a,^*, Yutian Wang ^b, Ulli Englert ^b, Khusnutdin M Shakhidoyatov ^a

PMCID: PMC3151818 PMID: 21836934

Abstract

In the crystal structure of the title two-dimensional network, [HgCl₂(C₁₁H₁₀N₂O)]_n, the asymmetric unit consists of HgCl₂ dumbbells and one molecule of the quinazoline unit. Pseudo-octahedrally coordinated Hg^II cations are chloride-bridged via a crystallographic inversion centre leading to different Hg—Cl bonds (short and long) and linked by other Cl atoms via translation along the a axis. The quinazoline ligands connect the Hg—Cl—Hg—Cl chains by N and O atoms along the b axis, forming the two-dimensional network structure. The crystal structure is stabilized by weak non-classical C—H⋯Cl hydrogen bonds and aromatic π–π stacking interactions [centroid–centroid distances = 3.942 (4) and 3.621 (4) Å].

Related literature

For the synthesis of the ligand, see: Chatterjee & Ganguly (1968 ▶). For the crystal structure of the ligand, see: Turgunov et al. (1995 ▶). For the crystal structure of the pure octahedral Hg^II ion and halide-bridged complex, see: Hu et al. (2007 ▶). For the crystal structure of a Hg^II complex with asymmetric Hg—Cl bonds, see: Batten et al. (2002 ▶); Hu et al. (2007 ▶); Merkens et al. (2010 ▶). For a general review of halide-bridged chain and crosslinking polymers, see: Englert (2010 ▶).

Experimental

Crystal data

[HgCl₂(C₁₁H₁₀N₂O)]
M _r = 457.70
Monoclinic,
a = 7.7275 (11) Å
b = 9.4705 (13) Å
c = 16.729 (2) Å
β = 101.416 (2)°
V = 1200.1 (3) Å³
Z = 4
Mo Kα radiation
μ = 13.25 mm⁻¹
T = 130 K
0.21 × 0.09 × 0.08 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.167, T _max = 0.417
13274 measured reflections
3014 independent reflections
2620 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.099
S = 1.20
3014 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 6.57 e Å⁻³
Δρ_min = −1.26 e Å⁻³

Data collection: SMART APEX (Bruker, 2000 ▶); 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: XP (Bruker, 1998 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811022471/si2358sup1.cif

e-67-0m953-sup1.cif^{(15.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811022471/si2358Isup2.hkl

e-67-0m953-Isup2.hkl^{(147.9KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Hg1—Cl1	2.3258 (16)
Hg1—Cl2	2.3302 (16)
Hg1—Cl1ⁱ	3.1301 (16)
Hg1—Cl2ⁱⁱ	3.0416 (16)
Hg1—O1ⁱⁱⁱ	2.775 (6)
Hg1—N1	2.649 (6)

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

Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C5—H5A⋯Cl1^iv	0.93	2.81	3.630 (8)	147
C10—H10B⋯Cl2^v	0.97	2.76	3.724 (9)	171

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Symmetry codes: (iv) Inline graphic ; (v) .

Acknowledgments

The authors gratefully acknowledge the DAAD for supporting this study.

supplementary crystallographic information

Comment

The title compound represents the first crystal structure of a complex with the heterocyclic ligand 1,2,3,9-tetrahydropyrrolo(2,1 - b)quinazolin-9-one; the uncoordinated organic molecule has been reported by Turgunov et al. (1995).

The asymmetric unit contains a slightly bent HgCl₂ moiety (Cl1—Hg1—Cl2 = 171.44 (6)°) and one ligand molecule (Fig.1) In the crystal each Hg^II cation is coordinated by four bridging chlorido ligands in the equatorial plane; one N- and one O-connected organic ligand occupy the axial positions of a distorted octahedron. The Hg—Cl bonds are asymmetric with two short and two longer distances (Table 1).

The bridging chlorido ligands form zigzag Hg—Cl—Hg—Cl ring chains in the direction of the shortest lattice parameter. Strongly asymmetric halide bridges are well established structural features in the coordination chemistry of divalent mercury (Batten et al., 2002; Hu et al., 2007; Merkens et al., 2010; Englert, 2010).

The chlorido-bridged Hg···Hg distances amount to 3.9342 (7) and 3.9442 (7) Å. As the result of halide bridging in the [100] and bridging of the ditopic organic ligand in the [010] direction, an overall two-dimensional sheet is formed which is depicted in Fig. 2.

The observed structure is stabilized by weak C—H···Cl hydrogen bonds (Table 2). Cooperative π–π stacking interactions between neighbouring quinazolone ring systems also contribute to the stability of this layer structure (Cg1···Cg1ⁱ=3.942 (4) Cg1···Cg2ⁱ=3.621 (4) Å, where Cg1 represents the centroid of the pyrimidinone and Cg2 that of the benzo ring centroid, (i): 2 - x,1 - y,-z).

The ligand molecule is essentially planar with a maximum deviation of 0.044 (7) Å for atom C10 and an r.m.s. deviation of 0.015 Å.

Experimental

A solution of 27.15 mg (0.1 mmol) of mercury (II) chloride in 2 ml water was added to a solution of 18.62 mg (0.1 mmol) of 1,2,3,9-tetrahydropyrrolo(2,1 - b)quinazolin-9-one in 2 ml acetone. The solution was allowed for slow evaporation at the room temperature. Colourless needle shaped crystals were obtained after several days.