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Acta Cryst. (2011). E67, m953-m954    [ doi:10.1107/S1600536811022471 ]

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

K. K. Turgunov, Y. Wang, U. Englert and K. M. Shakhidoyatov

Abstract top

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 HgII 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 [pi]-[pi] stacking interactions [centroid-centroid distances = 3.942 (4) and 3.621 (4) Å].

Comment top

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 HgII 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.

Related literature top

For the synthesis of the ligand, see Chatterjee et al. (1968). For the crystal structure of the ligand, see Turgunov et al. (1995). For the crystal structure of the pure octahedral HgII ion and halide- bridged complex, see Hu et al. (2007). For the crystal structure of a HgII 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 top

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.

Refinement top

Carbon-bound H atoms were positioned geometrically and treated as riding on their C atoms, with C—H distances of 0.93 Å (aromatic) and 0.97 Å (CH2) and were refined with Uiso(H)=1.2Ueq(C). After completion of the structure model, a difference Fourier synthesis resulted in a local maximum closer than 0.8 Å to Hg1.

Computing details top

Data collection: SMART APEX (Bruker, 2000); cell refinement: SAINT-Plus (Bruker, 1999); data reduction: SAINT-Plus (Bruker, 1999); 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).

Figures top
[Figure 1] Fig. 1. The asymmetric unit of the title coordination polymer (50% displacement ellipsoids).
[Figure 2] Fig. 2. View of a single two-dimensional sheet. (Hydrogen atoms are omitted for clarity).
Poly[di-µ-chlorido-µ-(1,2,3,9-tetrahydropyrrolo[2,1-b]quinazolin- 9-one-κ2N:O)-mercury(II)] top
Crystal data top
[HgCl2(C11H10N2O)]F(000) = 848
Mr = 457.70Dx = 2.533 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 3815 reflections
a = 7.7275 (11) Åθ = 2.2–28.3°
b = 9.4705 (13) ŵ = 13.25 mm−1
c = 16.729 (2) ÅT = 130 K
β = 101.416 (2)°Rod, colourless
V = 1200.1 (3) Å30.21 × 0.09 × 0.08 mm
Z = 4
Data collection top
Bruker SMART APEX
diffractometer		3014 independent reflections
Radiation source: fine-focus sealed tube2620 reflections with I > 2σ(I)
graphiteRint = 0.041
ω scansθmax = 28.5°, θmin = 2.5°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→10
Tmin = 0.167, Tmax = 0.417k = −12→12
13274 measured reflectionsl = −22→22
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099H-atom parameters constrained
S = 1.20 w = 1/[σ2(Fo2) + (0.0432P)2 + 2.8193P]
where P = (Fo2 + 2Fc2)/3
3014 reflections(Δ/σ)max = 0.001
154 parametersΔρmax = 6.57 e Å−3
0 restraintsΔρmin = −1.26 e Å−3
Crystal data top
[HgCl2(C11H10N2O)]V = 1200.1 (3) Å3
Mr = 457.70Z = 4
Monoclinic, P21/nMo Kα radiation
a = 7.7275 (11) ŵ = 13.25 mm−1
b = 9.4705 (13) ÅT = 130 K
c = 16.729 (2) Å0.21 × 0.09 × 0.08 mm
β = 101.416 (2)°
Data collection top
Bruker SMART APEX
diffractometer		3014 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2620 reflections with I > 2σ(I)
Tmin = 0.167, Tmax = 0.417Rint = 0.041
13274 measured reflectionsθmax = 28.5°
Refinement top
R[F2 > 2σ(F2)] = 0.042H-atom parameters constrained
wR(F2) = 0.099Δρmax = 6.57 e Å−3
S = 1.20Δρmin = −1.26 e Å−3
3014 reflectionsAbsolute structure: ?
154 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Hg10.75260 (3)0.03946 (3)0.005310 (12)0.02475 (11)
Cl10.9924 (2)0.02655 (19)0.11378 (9)0.0277 (3)
Cl20.5237 (2)0.01819 (19)−0.10788 (9)0.0288 (4)
O10.7419 (7)0.7485 (6)0.0235 (3)0.0439 (14)
N10.7546 (6)0.3191 (7)0.0057 (3)0.0248 (12)
C20.7279 (8)0.3824 (8)0.0697 (4)0.0264 (14)
N30.7223 (7)0.5265 (6)0.0757 (3)0.0245 (12)
C40.7484 (8)0.6201 (8)0.0148 (4)0.0286 (14)
C4A0.7784 (9)0.5509 (7)−0.0581 (4)0.0238 (14)
C50.8068 (9)0.6256 (8)−0.1257 (4)0.0320 (15)
H5A0.80740.7237−0.12400.038*
C60.8339 (9)0.5600 (8)−0.1943 (4)0.0321 (16)
H6A0.85100.6123−0.23910.038*
C70.8355 (9)0.4115 (7)−0.1964 (4)0.0249 (13)
H7A0.85340.3659−0.24340.030*
C80.8111 (8)0.3315 (7)−0.1301 (4)0.0249 (13)
H8A0.81430.2334−0.13200.030*
C8A0.7813 (8)0.4016 (7)−0.0596 (3)0.0193 (12)
C90.6954 (10)0.3200 (9)0.1470 (4)0.0374 (18)
H9A0.79240.25920.17160.045*
H9B0.58700.26540.13730.045*
C100.6806 (13)0.4488 (10)0.2024 (5)0.049 (2)
H10A0.56920.44600.22080.059*
H10B0.77570.44700.24990.059*
C110.6914 (10)0.5786 (8)0.1545 (4)0.0337 (17)
H11A0.58220.63190.14750.040*
H11B0.78800.63820.18100.040*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.02197 (15)0.03650 (19)0.01675 (14)0.00429 (11)0.00622 (9)0.00185 (9)
Cl10.0231 (7)0.0420 (10)0.0188 (7)0.0049 (7)0.0060 (5)0.0053 (6)
Cl20.0229 (8)0.0452 (10)0.0189 (7)−0.0008 (7)0.0055 (6)0.0021 (6)
O10.059 (4)0.035 (3)0.043 (3)0.009 (3)0.021 (3)−0.011 (3)
N10.028 (3)0.031 (3)0.016 (2)0.005 (2)0.005 (2)−0.0025 (19)
C20.024 (3)0.036 (4)0.019 (3)0.009 (3)0.005 (2)0.003 (3)
N30.021 (3)0.033 (3)0.020 (2)0.011 (2)0.004 (2)−0.002 (2)
C40.023 (3)0.035 (4)0.029 (3)0.004 (3)0.007 (2)−0.004 (3)
C4A0.021 (3)0.026 (4)0.023 (3)0.008 (3)0.000 (2)−0.002 (2)
C50.035 (4)0.031 (4)0.029 (3)−0.001 (3)0.005 (3)0.005 (3)
C60.033 (4)0.041 (5)0.024 (3)0.001 (3)0.008 (3)0.009 (3)
C70.026 (3)0.031 (4)0.018 (3)0.001 (3)0.006 (2)−0.001 (2)
C80.027 (3)0.025 (3)0.022 (3)0.005 (3)0.005 (2)0.000 (2)
C8A0.017 (3)0.023 (3)0.017 (2)0.004 (2)0.000 (2)0.002 (2)
C90.044 (4)0.052 (5)0.021 (3)0.014 (4)0.019 (3)0.004 (3)
C100.057 (5)0.069 (7)0.023 (3)−0.021 (5)0.014 (3)−0.016 (4)
C110.030 (4)0.047 (5)0.027 (3)0.010 (3)0.011 (3)−0.014 (3)
Geometric parameters (Å, °) top
Hg1—Cl12.3258 (16)C5—C61.357 (10)
Hg1—Cl22.3302 (16)C5—H5A0.93
Hg1—Cl1i3.1301 (16)C6—C71.407 (10)
Hg1—Cl2ii3.0416 (16)C6—H6A0.93
Hg1—O1iii2.775 (6)C7—C81.387 (9)
Hg1—N12.649 (6)C7—H7A0.93
O1—C41.227 (9)C8—C8A1.411 (8)
N1—C21.279 (8)C8—H8A0.93
N1—C8A1.392 (8)C9—C101.550 (11)
C2—N31.370 (9)C9—H9A0.97
C2—C91.488 (9)C9—H9B0.97
N3—C41.395 (9)C10—C111.479 (12)
N3—C111.471 (8)C10—H10A0.97
C4—C4A1.442 (9)C10—H10B0.97
C4A—C51.388 (9)C11—H11A0.97
C4A—C8A1.415 (10)C11—H11B0.97
Cl1—Hg1—Cl2171.44 (7)C6—C7—H7A119.3
Cl1—Hg1—N192.70 (11)C7—C8—C8A118.8 (6)
Cl2—Hg1—N195.27 (11)C7—C8—H8A120.6
C2—N1—C8A117.9 (6)C8A—C8—H8A120.6
C2—N1—Hg1118.0 (5)N1—C8A—C8117.8 (6)
C8A—N1—Hg1124.1 (4)N1—C8A—C4A122.8 (5)
N1—C2—N3122.7 (6)C8—C8A—C4A119.4 (5)
N1—C2—C9128.6 (7)C2—C9—C10104.6 (7)
N3—C2—C9108.6 (5)C2—C9—H9A110.8
C2—N3—C4124.6 (5)C10—C9—H9A110.8
C2—N3—C11114.4 (5)C2—C9—H9B110.8
C4—N3—C11121.0 (6)C10—C9—H9B110.8
O1—C4—N3121.9 (6)H9A—C9—H9B108.9
O1—C4—C4A124.6 (7)C11—C10—C9108.1 (6)
N3—C4—C4A113.6 (6)C11—C10—H10A110.1
C5—C4A—C8A119.2 (6)C9—C10—H10A110.1
C5—C4A—C4122.4 (7)C11—C10—H10B110.1
C8A—C4A—C4118.3 (6)C9—C10—H10B110.1
C6—C5—C4A122.1 (7)H10A—C10—H10B108.4
C6—C5—H5A118.9N3—C11—C10104.1 (6)
C4A—C5—H5A118.9N3—C11—H11A110.9
C5—C6—C7118.9 (6)C10—C11—H11A110.9
C5—C6—H6A120.6N3—C11—H11B110.9
C7—C6—H6A120.6C10—C11—H11B110.9
C8—C7—C6121.4 (6)H11A—C11—H11B109.0
C8—C7—H7A119.3
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+1, −y, −z; (iii) x, y−1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···Cl1iv0.932.813.630 (8)147.
C10—H10B···Cl2v0.972.763.724 (9)171.
Symmetry codes: (iv) −x+2, −y+1, −z; (v) x+1/2, −y+1/2, z+1/2.
Table 1
Selected geometric parameters (Å) top
Hg1—Cl12.3258 (16)Hg1—Cl2ii3.0416 (16)
Hg1—Cl22.3302 (16)Hg1—O1iii2.775 (6)
Hg1—Cl1i3.1301 (16)Hg1—N12.649 (6)
Symmetry codes: (i) −x+2, −y, −z; (ii) −x+1, −y, −z; (iii) x, y−1, z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C5—H5A···Cl1iv0.932.813.630 (8)147.
C10—H10B···Cl2v0.972.763.724 (9)171.
Symmetry codes: (iv) −x+2, −y+1, −z; (v) x+1/2, −y+1/2, z+1/2.
Acknowledgements top

The authors gratefully acknowledge the DAAD for supporting this study.

references
References top

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