supplementary materials


br2220 scheme

Acta Cryst. (2013). E69, m109    [ doi:10.1107/S1600536813001086 ]

Dichlorido(2,9-dimethyl-1,10-phenanthroline-[kappa]2N,N')mercury(II)

I. Warad, M. Al-Noaimi, S. F. Haddad and R. Othman

Abstract top

The title compound, [HgCl2(C14H12N2)], consists of one 2,9-dimethyl-1,10-phenanthroline (dmphen) ligand chelating the HgII ion and two chloride ligands coordinating to the HgII ion, forming a distorted tetrahedral environment. The dmphen ligand is nearly planar (r.m.s. deviation = 0.0225 Å). The dihedral angle between the normal to the plane defined by the HgII atom and the two Cl atoms and the normal to the plane of the dmphen ring is 81.8 (1)°.

Comment top

The coordination chemistry of mercury(II) with N-donor ligands is of interest due to applications as solid-state materials (Ramazani et al., 2005; Mahjoub et al., 2004). Hg(II) complexes with bidentate ligands have been obtained in which Hg(II) adopts higher coordination numbers such as complexes of 1,10-phenanthroline (Canty & Maker, 1976) and N-substituted pyrazole (Canty & Lee, 1982). The molecular structure of [HgCl2(C14H12N2)], along with the numbering scheme is shown in Fig. 1. HgCl2 is chelated by the bidentate phenanthroline molecule and that the coordination of the nitrogen and chlorine atoms about the Hg atom is essentially a distorted tetrahedral environment (Fig. 1).

Related literature top

For related structures, see Alizadeh (2009); Alizadeh et al. (2009); Wang & Zhong (2009); Warad et al. (2011). For properties and application of mercury(II) complexes, see Ramazani et al. (2005); Mahjoub et al. (2004); Canty & Maker, (1976); Canty & Lee (1982).

Experimental top

The desired complex was prepared by mixting of mercury chloride (HgCl2, 39.7 mg,0.14 mmol) in methanol (10 ml) with dmphen (32.0 mg, 0.15 mmol) in dichloromethane (5 ml) is stirred for one houre at room temperature. The obtained solution was concentrated to about 2 ml underreduced pressure and mixed to 30 ml of diethyl ether. The white precipitate was filtered and dried. suitable colourless crystals were obtained by slow diffusion of diethyl ether into a solution of the complex in dichloromethane.

Refinement top

All nonhydrogen atoms were refined anisotropically.H atoms were positioned geometrically, with C-H = 0.93 and 0.96 Å for aromatic and methyl H, respectively, and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). Highest difference peak and hole are 1.81 and -1.83e/Å3 close to the Hg atom.

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. An ORTEP (Burnett & Johnson, 1996) view of Hg(Cl)2(dmphen). Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
Dichlorido(2,9-dimethyl-1,10-phenanthroline-κ2N,N')mercury(II) top
Crystal data top
[HgCl2(C14H12N2)]F(000) = 896
Mr = 479.75Dx = 2.178 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1534 reflections
a = 7.5732 (13) Åθ = 2.9–29.0°
b = 10.3733 (16) ŵ = 10.87 mm1
c = 18.673 (2) ÅT = 293 K
β = 94.308 (12)°Block, colourless
V = 1462.8 (4) Å30.22 × 0.20 × 0.18 mm
Z = 4
Data collection top
Agilent Xcalibur Eos
diffractometer
2564 independent reflections
Radiation source: Enhance (Mo) X-ray Source1758 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.061
Detector resolution: 16.0534 pixels mm-1θmax = 25.0°, θmin = 2.9°
ω scansh = 97
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
k = 1212
Tmin = 0.106, Tmax = 0.140l = 1622
5483 measured reflections
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)] = 0.051Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.128H-atom parameters constrained
S = 0.99 w = 1/[σ2(Fo2) + (0.0521P)2]
where P = (Fo2 + 2Fc2)/3
2564 reflections(Δ/σ)max < 0.001
174 parametersΔρmax = 1.81 e Å3
0 restraintsΔρmin = 1.83 e Å3
Crystal data top
[HgCl2(C14H12N2)]V = 1462.8 (4) Å3
Mr = 479.75Z = 4
Monoclinic, P21/cMo Kα radiation
a = 7.5732 (13) ŵ = 10.87 mm1
b = 10.3733 (16) ÅT = 293 K
c = 18.673 (2) Å0.22 × 0.20 × 0.18 mm
β = 94.308 (12)°
Data collection top
Agilent Xcalibur Eos
diffractometer
2564 independent reflections
Absorption correction: multi-scan
(CrysAlis PRO; Agilent, 2011)
1758 reflections with I > 2σ(I)
Tmin = 0.106, Tmax = 0.140Rint = 0.061
5483 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.051H-atom parameters constrained
wR(F2) = 0.128Δρmax = 1.81 e Å3
S = 0.99Δρmin = 1.83 e Å3
2564 reflectionsAbsolute structure: ?
174 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
Hg10.21008 (6)0.28289 (4)0.39470 (2)0.0597 (2)
Cl10.0404 (4)0.3290 (4)0.31096 (16)0.0818 (10)
Cl20.4266 (5)0.4523 (3)0.39503 (19)0.0871 (11)
C50.3385 (16)0.2144 (11)0.4986 (7)0.063 (3)
H5A0.37360.30020.49750.076*
N10.2952 (11)0.0704 (7)0.3787 (4)0.047 (2)
C10.3465 (14)0.0196 (11)0.3185 (6)0.057 (3)
C100.1290 (15)0.2260 (10)0.5625 (7)0.055 (3)
C110.2939 (12)0.0049 (11)0.4375 (5)0.048 (2)
C30.3905 (15)0.1866 (12)0.3704 (7)0.060 (3)
H3A0.42100.27310.36700.072*
C80.1676 (15)0.0244 (12)0.6240 (6)0.067 (3)
H8A0.16360.02470.66550.080*
C120.2350 (11)0.0470 (11)0.5026 (5)0.048 (3)
N20.1849 (11)0.1747 (8)0.5019 (4)0.045 (2)
C70.2276 (13)0.0328 (10)0.5619 (6)0.052 (3)
C140.0775 (16)0.3651 (12)0.5595 (6)0.073 (4)
H14A0.18220.41760.56150.110*
H14B0.01000.38530.59950.110*
H14C0.00730.38190.51550.110*
C40.3430 (13)0.1380 (10)0.4363 (6)0.052 (3)
C20.3929 (15)0.1104 (11)0.3118 (7)0.066 (3)
H2A0.42450.14340.26830.080*
C60.2834 (14)0.1637 (11)0.5598 (7)0.062 (3)
H6A0.28200.21470.60070.074*
C90.1155 (14)0.1497 (14)0.6246 (5)0.061 (3)
H9A0.07150.18500.66540.074*
C130.3475 (18)0.1076 (12)0.2547 (6)0.083 (4)
H13A0.34490.05720.21160.124*
H13B0.45280.15940.25870.124*
H13C0.24530.16260.25320.124*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.0813 (4)0.0419 (4)0.0565 (3)0.0057 (2)0.0083 (3)0.00836 (19)
Cl10.075 (2)0.111 (3)0.0590 (19)0.016 (2)0.0022 (15)0.0250 (18)
Cl20.106 (3)0.0474 (18)0.107 (3)0.0145 (19)0.003 (2)0.0152 (18)
C50.070 (8)0.046 (8)0.075 (9)0.002 (6)0.009 (6)0.023 (7)
N10.056 (5)0.033 (5)0.051 (5)0.001 (4)0.002 (4)0.003 (4)
C10.061 (7)0.052 (7)0.059 (7)0.003 (6)0.014 (5)0.003 (6)
C100.053 (7)0.047 (7)0.065 (8)0.003 (5)0.007 (5)0.008 (6)
C110.037 (6)0.056 (7)0.049 (6)0.003 (5)0.001 (4)0.003 (6)
C30.050 (7)0.049 (7)0.080 (9)0.007 (5)0.004 (6)0.003 (7)
C80.071 (8)0.066 (8)0.062 (8)0.016 (7)0.002 (6)0.017 (7)
C120.020 (5)0.060 (7)0.062 (7)0.006 (5)0.007 (4)0.008 (6)
N20.051 (5)0.043 (5)0.041 (5)0.006 (4)0.004 (4)0.002 (4)
C70.062 (7)0.038 (6)0.055 (7)0.007 (5)0.001 (5)0.015 (5)
C140.078 (9)0.088 (10)0.055 (7)0.002 (8)0.015 (6)0.021 (7)
C40.042 (6)0.036 (6)0.077 (8)0.007 (5)0.000 (5)0.005 (6)
C20.076 (9)0.057 (8)0.065 (8)0.015 (7)0.001 (6)0.016 (7)
C60.048 (7)0.060 (8)0.075 (9)0.014 (6)0.006 (6)0.030 (7)
C90.051 (7)0.099 (10)0.035 (6)0.009 (7)0.007 (4)0.005 (7)
C130.133 (13)0.059 (8)0.061 (8)0.001 (8)0.031 (8)0.006 (7)
Geometric parameters (Å, º) top
Hg1—N22.314 (8)C3—C41.401 (15)
Hg1—N12.322 (8)C3—H3A0.9300
Hg1—Cl22.403 (3)C8—C91.359 (16)
Hg1—Cl12.414 (3)C8—C71.408 (15)
C5—C61.352 (16)C8—H8A0.9300
C5—C41.410 (15)C12—N21.378 (13)
C5—H5A0.9300C12—C71.386 (13)
N1—C11.326 (12)C7—C61.424 (15)
N1—C111.348 (12)C14—H14A0.9600
C1—C21.402 (15)C14—H14B0.9600
C1—C131.501 (15)C14—H14C0.9600
C10—N21.348 (13)C2—H2A0.9300
C10—C91.414 (15)C6—H6A0.9300
C10—C141.494 (15)C9—H9A0.9300
C11—C41.430 (14)C13—H13A0.9600
C11—C121.432 (13)C13—H13B0.9600
C3—C21.350 (16)C13—H13C0.9600
N2—Hg1—N172.1 (3)C10—N2—C12118.3 (9)
N2—Hg1—Cl2116.9 (2)C10—N2—Hg1125.9 (7)
N1—Hg1—Cl2119.9 (2)C12—N2—Hg1115.8 (6)
N2—Hg1—Cl1123.0 (2)C12—C7—C8116.1 (10)
N1—Hg1—Cl1108.5 (2)C12—C7—C6121.2 (11)
Cl2—Hg1—Cl1111.07 (13)C8—C7—C6122.6 (10)
C6—C5—C4120.5 (11)C10—C14—H14A109.5
C6—C5—H5A119.8C10—C14—H14B109.5
C4—C5—H5A119.8H14A—C14—H14B109.5
C1—N1—C11118.8 (9)C10—C14—H14C109.5
C1—N1—Hg1126.0 (7)H14A—C14—H14C109.5
C11—N1—Hg1115.2 (7)H14B—C14—H14C109.5
N1—C1—C2123.3 (10)C3—C4—C5123.1 (10)
N1—C1—C13116.8 (10)C3—C4—C11116.5 (10)
C2—C1—C13119.9 (10)C5—C4—C11120.4 (10)
N2—C10—C9120.9 (10)C3—C2—C1118.2 (11)
N2—C10—C14116.5 (10)C3—C2—H2A120.9
C9—C10—C14122.5 (10)C1—C2—H2A120.9
N1—C11—C4121.9 (9)C5—C6—C7120.3 (11)
N1—C11—C12119.7 (10)C5—C6—H6A119.8
C4—C11—C12118.4 (10)C7—C6—H6A119.8
C2—C3—C4121.4 (11)C8—C9—C10119.3 (11)
C2—C3—H3A119.3C8—C9—H9A120.3
C4—C3—H3A119.3C10—C9—H9A120.3
C9—C8—C7121.5 (11)C1—C13—H13A109.5
C9—C8—H8A119.3C1—C13—H13B109.5
C7—C8—H8A119.3H13A—C13—H13B109.5
N2—C12—C7123.7 (10)C1—C13—H13C109.5
N2—C12—C11117.1 (9)H13A—C13—H13C109.5
C7—C12—C11119.1 (10)H13B—C13—H13C109.5
Acknowledgements top

The project was supported by King Saud University (KSA) and Hashemite University (Jordan). The X-ray structural work was done at Hamdi Mango Center for Scientific Research at The University of Jordan, Amman 11942, Jordan.

references
References top

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England

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