Dichlorido(2,9-dimethyl-1,10-phenanthroline-κ2N,N′)mercury(II)

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

doi:10.1107/S1600536813001086

metal-organic compounds

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ISSN: 2056-9890

Volume 69| Part 2| February 2013| Page m109

doi:10.1107/S1600536813001086

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Dichlorido(2,9-dimethyl-1,10-phenanthroline-κ²N,N′)mercury(II)

Ismail Warad,^a Mousa Al-Noaimi,^b ^* Salim F. Haddad ^c and Rema Othman ^d

^aDepartment of Chemistry, AN-Najah National University, Nablus, Palestinian Territories, ^bDepartment of Chemistry, Hashemite University, Zarqa 13115, Jordan, ^cDepartment of Chemistry, The University of Jordan, Amman 11942, Jordan, and ^dLanguage Centre, Hashemite University, Zarqa 13115, Jordan
^*Correspondence e-mail: manoaimi@hu.edu.jo

(Received 2 January 2013; accepted 11 January 2013; online 19 January 2013)

The title compound, [HgCl₂(C₁₄H₁₂N₂)], consists of one 2,9-dimethyl-1,10-phenanthroline (dmphen) ligand chelating the Hg^II ion and two chloride ligands coordinating to the Hg^II 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 Hg^II atom and the two Cl atoms and the normal to the plane of the dmphen ring is 81.8 (1)°.

Related literature

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

Crystal data

[HgCl₂(C₁₄H₁₂N₂)]
M_r = 479.75
Monoclinic, P 2₁ /c
a = 7.5732 (13) Å
b = 10.3733 (16) Å
c = 18.673 (2) Å
β = 94.308 (12)°
V = 1462.8 (4) Å³
Z = 4
Mo Kα radiation
μ = 10.87 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.18 mm

Data collection

Agilent Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ) T_min = 0.106, T_max = 0.140
5483 measured reflections
2564 independent reflections
1758 reflections with I > 2σ(I)
R_int = 0.061

Refinement

R[F² > 2σ(F²)] = 0.051
wR(F²) = 0.128
S = 0.99
2564 reflections
174 parameters
H-atom parameters constrained
Δρ_max = 1.81 e Å⁻³
Δρ_min = −1.83 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; 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).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813001086/br2220sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813001086/br2220Isup2.hkl

checkCIF report

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.

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

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
M_r = 479.75	D_x = 2.178 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 1534 reflections
a = 7.5732 (13) Å	θ = 2.9–29.0°
b = 10.3733 (16) Å	µ = 10.87 mm⁻¹
c = 18.673 (2) Å	T = 293 K
β = 94.308 (12)°	Block, colourless
V = 1462.8 (4) Å³	0.22 × 0.20 × 0.18 mm
Z = 4

Data collection top

Agilent Xcalibur Eos diffractometer	2564 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1758 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.061
Detector resolution: 16.0534 pixels mm^-1	θ_max = 25.0°, θ_min = 2.9°
ω scans	h = −9→7
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011)	k = −12→12
T_min = 0.106, T_max = 0.140	l = −16→22
5483 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.128	H-atom parameters constrained
S = 0.99	w = 1/[σ²(F_o²) + (0.0521P)²] where P = (F_o² + 2F_c²)/3
2564 reflections	(Δ/σ)_max < 0.001
174 parameters	Δρ_max = 1.81 e Å⁻³
0 restraints	Δρ_min = −1.83 e Å⁻³

Crystal data top

[HgCl₂(C₁₄H₁₂N₂)]	V = 1462.8 (4) Å³
M_r = 479.75	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.5732 (13) Å	µ = 10.87 mm⁻¹
b = 10.3733 (16) Å	T = 293 K
c = 18.673 (2) Å	0.22 × 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)
T_min = 0.106, T_max = 0.140	R_int = 0.061
5483 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	0 restraints
wR(F²) = 0.128	H-atom parameters constrained
S = 0.99	Δρ_max = 1.81 e Å⁻³
2564 reflections	Δρ_min = −1.83 e Å⁻³
174 parameters

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

	x	y	z	U_iso*/U_eq
Hg1	0.21008 (6)	0.28289 (4)	0.39470 (2)	0.0597 (2)
Cl1	−0.0404 (4)	0.3290 (4)	0.31096 (16)	0.0818 (10)
Cl2	0.4266 (5)	0.4523 (3)	0.39503 (19)	0.0871 (11)
C5	0.3385 (16)	−0.2144 (11)	0.4986 (7)	0.063 (3)
H5A	0.3736	−0.3002	0.4975	0.076*
N1	0.2952 (11)	0.0704 (7)	0.3787 (4)	0.047 (2)
C1	0.3465 (14)	0.0196 (11)	0.3185 (6)	0.057 (3)
C10	0.1290 (15)	0.2260 (10)	0.5625 (7)	0.055 (3)
C11	0.2939 (12)	−0.0049 (11)	0.4375 (5)	0.048 (2)
C3	0.3905 (15)	−0.1866 (12)	0.3704 (7)	0.060 (3)
H3A	0.4210	−0.2731	0.3670	0.072*
C8	0.1676 (15)	0.0244 (12)	0.6240 (6)	0.067 (3)
H8A	0.1636	−0.0247	0.6655	0.080*
C12	0.2350 (11)	0.0470 (11)	0.5026 (5)	0.048 (3)
N2	0.1849 (11)	0.1747 (8)	0.5019 (4)	0.045 (2)
C7	0.2276 (13)	−0.0328 (10)	0.5619 (6)	0.052 (3)
C14	0.0775 (16)	0.3651 (12)	0.5595 (6)	0.073 (4)
H14A	0.1822	0.4176	0.5615	0.110*
H14B	0.0100	0.3853	0.5995	0.110*
H14C	0.0073	0.3819	0.5155	0.110*
C4	0.3430 (13)	−0.1380 (10)	0.4363 (6)	0.052 (3)
C2	0.3929 (15)	−0.1104 (11)	0.3118 (7)	0.066 (3)
H2A	0.4245	−0.1434	0.2683	0.080*
C6	0.2834 (14)	−0.1637 (11)	0.5598 (7)	0.062 (3)
H6A	0.2820	−0.2147	0.6007	0.074*
C9	0.1155 (14)	0.1497 (14)	0.6246 (5)	0.061 (3)
H9A	0.0715	0.1850	0.6654	0.074*
C13	0.3475 (18)	0.1076 (12)	0.2547 (6)	0.083 (4)
H13A	0.3449	0.0572	0.2116	0.124*
H13B	0.4528	0.1594	0.2587	0.124*
H13C	0.2453	0.1626	0.2532	0.124*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.0813 (4)	0.0419 (4)	0.0565 (3)	0.0057 (2)	0.0083 (3)	0.00836 (19)
Cl1	0.075 (2)	0.111 (3)	0.0590 (19)	0.016 (2)	0.0022 (15)	0.0250 (18)
Cl2	0.106 (3)	0.0474 (18)	0.107 (3)	−0.0145 (19)	0.003 (2)	0.0152 (18)
C5	0.070 (8)	0.046 (8)	0.075 (9)	−0.002 (6)	0.009 (6)	0.023 (7)
N1	0.056 (5)	0.033 (5)	0.051 (5)	−0.001 (4)	0.002 (4)	−0.003 (4)
C1	0.061 (7)	0.052 (7)	0.059 (7)	0.003 (6)	0.014 (5)	0.003 (6)
C10	0.053 (7)	0.047 (7)	0.065 (8)	0.003 (5)	0.007 (5)	−0.008 (6)
C11	0.037 (6)	0.056 (7)	0.049 (6)	−0.003 (5)	−0.001 (4)	0.003 (6)
C3	0.050 (7)	0.049 (7)	0.080 (9)	0.007 (5)	−0.004 (6)	−0.003 (7)
C8	0.071 (8)	0.066 (8)	0.062 (8)	−0.016 (7)	−0.002 (6)	0.017 (7)
C12	0.020 (5)	0.060 (7)	0.062 (7)	−0.006 (5)	−0.007 (4)	0.008 (6)
N2	0.051 (5)	0.043 (5)	0.041 (5)	−0.006 (4)	0.004 (4)	−0.002 (4)
C7	0.062 (7)	0.038 (6)	0.055 (7)	−0.007 (5)	0.001 (5)	0.015 (5)
C14	0.078 (9)	0.088 (10)	0.055 (7)	0.002 (8)	0.015 (6)	−0.021 (7)
C4	0.042 (6)	0.036 (6)	0.077 (8)	−0.007 (5)	0.000 (5)	0.005 (6)
C2	0.076 (9)	0.057 (8)	0.065 (8)	0.015 (7)	−0.001 (6)	−0.016 (7)
C6	0.048 (7)	0.060 (8)	0.075 (9)	−0.014 (6)	−0.006 (6)	0.030 (7)
C9	0.051 (7)	0.099 (10)	0.035 (6)	−0.009 (7)	0.007 (4)	0.005 (7)
C13	0.133 (13)	0.059 (8)	0.061 (8)	0.001 (8)	0.031 (8)	0.006 (7)

Geometric parameters (Å, º) top

Hg1—N2	2.314 (8)	C3—C4	1.401 (15)
Hg1—N1	2.322 (8)	C3—H3A	0.9300
Hg1—Cl2	2.403 (3)	C8—C9	1.359 (16)
Hg1—Cl1	2.414 (3)	C8—C7	1.408 (15)
C5—C6	1.352 (16)	C8—H8A	0.9300
C5—C4	1.410 (15)	C12—N2	1.378 (13)
C5—H5A	0.9300	C12—C7	1.386 (13)
N1—C1	1.326 (12)	C7—C6	1.424 (15)
N1—C11	1.348 (12)	C14—H14A	0.9600
C1—C2	1.402 (15)	C14—H14B	0.9600
C1—C13	1.501 (15)	C14—H14C	0.9600
C10—N2	1.348 (13)	C2—H2A	0.9300
C10—C9	1.414 (15)	C6—H6A	0.9300
C10—C14	1.494 (15)	C9—H9A	0.9300
C11—C4	1.430 (14)	C13—H13A	0.9600
C11—C12	1.432 (13)	C13—H13B	0.9600
C3—C2	1.350 (16)	C13—H13C	0.9600

N2—Hg1—N1	72.1 (3)	C10—N2—C12	118.3 (9)
N2—Hg1—Cl2	116.9 (2)	C10—N2—Hg1	125.9 (7)
N1—Hg1—Cl2	119.9 (2)	C12—N2—Hg1	115.8 (6)
N2—Hg1—Cl1	123.0 (2)	C12—C7—C8	116.1 (10)
N1—Hg1—Cl1	108.5 (2)	C12—C7—C6	121.2 (11)
Cl2—Hg1—Cl1	111.07 (13)	C8—C7—C6	122.6 (10)
C6—C5—C4	120.5 (11)	C10—C14—H14A	109.5
C6—C5—H5A	119.8	C10—C14—H14B	109.5
C4—C5—H5A	119.8	H14A—C14—H14B	109.5
C1—N1—C11	118.8 (9)	C10—C14—H14C	109.5
C1—N1—Hg1	126.0 (7)	H14A—C14—H14C	109.5
C11—N1—Hg1	115.2 (7)	H14B—C14—H14C	109.5
N1—C1—C2	123.3 (10)	C3—C4—C5	123.1 (10)
N1—C1—C13	116.8 (10)	C3—C4—C11	116.5 (10)
C2—C1—C13	119.9 (10)	C5—C4—C11	120.4 (10)
N2—C10—C9	120.9 (10)	C3—C2—C1	118.2 (11)
N2—C10—C14	116.5 (10)	C3—C2—H2A	120.9
C9—C10—C14	122.5 (10)	C1—C2—H2A	120.9
N1—C11—C4	121.9 (9)	C5—C6—C7	120.3 (11)
N1—C11—C12	119.7 (10)	C5—C6—H6A	119.8
C4—C11—C12	118.4 (10)	C7—C6—H6A	119.8
C2—C3—C4	121.4 (11)	C8—C9—C10	119.3 (11)
C2—C3—H3A	119.3	C8—C9—H9A	120.3
C4—C3—H3A	119.3	C10—C9—H9A	120.3
C9—C8—C7	121.5 (11)	C1—C13—H13A	109.5
C9—C8—H8A	119.3	C1—C13—H13B	109.5
C7—C8—H8A	119.3	H13A—C13—H13B	109.5
N2—C12—C7	123.7 (10)	C1—C13—H13C	109.5
N2—C12—C11	117.1 (9)	H13A—C13—H13C	109.5
C7—C12—C11	119.1 (10)	H13B—C13—H13C	109.5

Experimental details

Crystal data
Chemical formula	[HgCl₂(C₁₄H₁₂N₂)]
M_r	479.75
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	293
a, b, c (Å)	7.5732 (13), 10.3733 (16), 18.673 (2)
β (°)	94.308 (12)
V (Å³)	1462.8 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	10.87
Crystal size (mm)	0.22 × 0.20 × 0.18

Data collection
Diffractometer	Agilent Xcalibur Eos diffractometer
Absorption correction	Multi-scan (CrysAlis PRO; Agilent, 2011)
T_min, T_max	0.106, 0.140
No. of measured, independent and observed [I > 2σ(I)] reflections	5483, 2564, 1758
R_int	0.061
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.051, 0.128, 0.99
No. of reflections	2564
No. of parameters	174
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.81, −1.83

Computer programs: CrysAlis PRO (Agilent, 2011), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), SHELXTL (Sheldrick, 2008).

Acknowledgements

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

Agilent (2011). CrysAlis PRO. Agilent Technologies, Yarnton, England. Google Scholar
Alizadeh, R. (2009). Acta Cryst. E65, m817–m818. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Alizadeh, R., Heidari, A., Ahmadi, R. & Amani, V. (2009). Acta Cryst. E65, m483–m484. Web of Science CSD CrossRef IUCr Journals Google Scholar
Burnett, M. N. & Johnson, C. K. (1996). ORTEPIII. Report ORNL-6895. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Canty, A. J. & Lee, C. V. (1982). Organometallics, 1, 1063–1066. CrossRef CAS Web of Science Google Scholar
Canty, A. J. & Maker, A. (1976). Inorg. Chem. 15, 425–430. CrossRef CAS Web of Science Google Scholar
Mahjoub, A., Morsali, A. & Nejad, R. (2004). Z. Naturforsch. Teil B, 59, 1109–1113. CAS Google Scholar
Ramazani, A., Morsali, A., Dolatyari, L. & Ganjeie, B. (2005). Z. Naturforsch. Teil B, 60, 289–293. CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, B. S. & Zhong, H. (2009). Acta Cryst. E65, m1156. Web of Science CSD CrossRef IUCr Journals Google Scholar
Warad, I., Boshaala, A., Al-Resayes, S. I., Al-Deyab, S. S. & Rzaigui, M. (2011). Acta Cryst. E67, m1650. Web of Science CSD CrossRef IUCr Journals Google Scholar