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Acta Cryst. (2009). E65, m9-m10    [ doi:10.1107/S1600536808040294 ]

Dichlorido(di-2-pyridylamine)mercury(II)

M. Yousefi, M. R. Allahgholi Ghasri, A. Heidari and V. Amani

Abstract top

In the molecule of the title compound, [HgCl2(C10H9N3)], the HgII atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from the chelating di-2-pyridylamine ligand and by two Cl atoms. In the crystal structure, intermolecular N-H...Cl hydrogen bonds link the molecules into centrosymmetric dimers. There is a [pi]-[pi] contact between the pyridine rings [centroid-centroid distance = 3.896 (5) Å].

Comment top

Recently, we reported the synthes and crystal structures of [Hg(NH(py)2)Br2], (II), (Kalateh, Norouzi et al., 2008), [Hg(4,4'-dmbpy)I2], (III), (Yousefi, Tadayon Pour et al., 2008), [Hg(5,5'-dmbpy)I2], (IV), (Tadayon Pour et al., 2008), [Hg(dmphen)I2], (V), (Yousefi, Rashidi Vahid et al., 2008), {[HgCl(dm4bt)]2(µ-Cl)2}, (VI), (Khavasi et al., 2008), [Hg(6-mbpy)Cl2], (VII), (Ahmadi et al., 2008) and [{HgBr(4,4'-dmbpy)}2(µ-Br)2], (VIII), (Kalateh, Ebadi et al., 2008) [where NH(py)2 is di-2-pyridylamine, 4,4'-dmbpy is 4,4'-dimethyl-2,2'-bipyridine, 5,5'-dmbpy is 5,5'-dimethyl-2,2'-bipyridine, 6-mbpy is 6-methyl-2,2'-bipyridine, dmphen is 4,7-diphenyl- 1,10-phenanthroline and dm4bt is 2,2'-dimethyl-4,4'-bithiazole].

There are several HgII complexes, with formula, [Hg(N—N)Cl2], such as [Hg(bipy)Cl2], (IX), and [Hg(bipy)Cl2][HgCl2], (X), (Chen et al., 2006) and [Hg(dpdmbip) Cl2].CH2Cl2, (XI), (Liu et al., 2004) [where bipy is 2,2'-bipyridine and dpdmbip is 4,4'-diphenyl-6,6'-dimethyl-2,2'-bipyrimidine] have been synthesized and characterized by single-crystal X-ray diffraction methods. We report herein the synthesis and crystal structure of the title compound, (I).

In the title compound, (Fig. 1), the HgII atom is four-coordinated in a distorted tetrahedral configuration by two N atoms from di-2-pyridylamine and two Cl atoms. The Hg-Cl and Hg-N bond lengths (Allen et al., 1987) and angles (Table 1) are within normal ranges.

In the crystal structure, intermolecular N-H···Cl hydrogen bonds (Table 2) link the molecules into centrosymmetric dimers, in which they may be effective in the stabilization of the crystal structure (Fig. 2). The π-π contact between the pyridine rings, Cg2···Cg3i [symmetry code: (i) -x, 1 - y, 1 - z, where Cg2 and Cg3 are centroids of the rings A (N1/C1-C5) and B (N3/C6-C10), respectively] may further stabilize the structure, with centroid-centroid distance of 3.896 (5)%A.

Related literature top

For related literature, see: Ahmadi et al. (2008); Kalateh, Ebadi et al. (2008); Kalateh, Norouzi et al. (2008); Khavasi et al. (2008); Tadayon Pour et al. (2008); Yousefi, Rashidi Vahid et al. (2008); Yousefi, Tadayon Pour et al. (2008). For related structures, see: Chen et al. (2006); Liu et al. (2004). For bond-length data, see: Allen et al. (1987).

Experimental top

For the preparation of the title compound, (I), a solution of di-2-pyridylamine (0.25 g, 1.43 mmol) in methanol (20 ml) was added to a solution of HgCl2 (0.39 g, 1.43 mmol) in acetonitrile (20 ml) and the resulting colorless solution was stirred for 20 min at 313 K. This solution was left to evaporate slowly at room temperature. After one week, colorless block crystals of the title compound were isolated (yield; 0.47 g, 74.3%).

Refinement top

H2B atom (for NH) was located in difference synthesis and refined isotropically [N-H = 0.95 (14) Å and Uiso(H) = 0.10 (4) Å2]. The remaining H atoms were positioned geometrically, with C-H = 0.93 Å for aromatic H and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 40% probability level.
[Figure 2] Fig. 2. A packing diagram of the title compound. Hydrogen bonds are shown as dashed lines.
Dichlorido(di-2-pyridylamine)mercury(II) top
Crystal data top
[HgCl2(C10H9N3)]Z = 2
Mr = 442.69F(000) = 408
Triclinic, P1Dx = 2.437 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.0268 (12) ÅCell parameters from 1652 reflections
b = 8.6127 (11) Åθ = 2.6–29.2°
c = 9.6118 (14) ŵ = 13.17 mm−1
α = 110.606 (11)°T = 298 K
β = 98.958 (12)°Block, colorless
γ = 96.862 (11)°0.24 × 0.21 × 0.15 mm
V = 603.38 (15) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer		3214 independent reflections
Radiation source: fine-focus sealed tube2806 reflections with I > 2σ(I)
graphiteRint = 0.069
φ and ω scansθmax = 29.2°, θmin = 2.6°
Absorption correction: multi scan
(SADABS; Sheldrick, 1998)		h = −10→10
Tmin = 0.061, Tmax = 0.142k = −11→11
7105 measured reflectionsl = −13→12
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.126 w = 1/[σ2(Fo2) + (0.075P)2 + 0.8992P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.026
3214 reflectionsΔρmax = 2.43 e Å−3
150 parametersΔρmin = −2.08 e Å−3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.048 (3)
Crystal data top
[HgCl2(C10H9N3)]γ = 96.862 (11)°
Mr = 442.69V = 603.38 (15) Å3
Triclinic, P1Z = 2
a = 8.0268 (12) ÅMo Kα radiation
b = 8.6127 (11) ŵ = 13.17 mm−1
c = 9.6118 (14) ÅT = 298 K
α = 110.606 (11)°0.24 × 0.21 × 0.15 mm
β = 98.958 (12)°
Data collection top
Bruker SMART CCD area-detector
diffractometer		3214 independent reflections
Absorption correction: multi scan
(SADABS; Sheldrick, 1998)		2806 reflections with I > 2σ(I)
Tmin = 0.061, Tmax = 0.142Rint = 0.069
7105 measured reflectionsθmax = 29.2°
Refinement top
R[F2 > 2σ(F2)] = 0.046H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.126Δρmax = 2.43 e Å−3
S = 1.05Δρmin = −2.08 e Å−3
3214 reflectionsAbsolute structure: ?
150 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
Hg10.21151 (4)0.24646 (4)0.63832 (4)0.06055 (18)
Cl10.4456 (3)0.1830 (3)0.7818 (3)0.0683 (5)
Cl2−0.0856 (2)0.1450 (2)0.6448 (2)0.0553 (4)
N10.1944 (8)0.5364 (8)0.7382 (7)0.0497 (12)
N20.2047 (8)0.5833 (7)0.5110 (6)0.0459 (11)
N30.2876 (7)0.3143 (7)0.4439 (7)0.0447 (11)
C10.1758 (12)0.5982 (12)0.8836 (9)0.0636 (19)
H10.18620.52940.93930.076*
C20.1428 (12)0.7553 (13)0.9537 (9)0.069 (2)
H20.12850.79201.05370.083*
H2B0.186 (18)0.662 (18)0.464 (16)0.10 (4)*
C30.1312 (11)0.8591 (11)0.8713 (9)0.0624 (18)
H30.11150.96830.91570.075*
C40.1493 (9)0.7975 (9)0.7231 (8)0.0514 (14)
H40.13790.86350.66490.062*
C50.1848 (7)0.6352 (7)0.6597 (7)0.0398 (11)
C60.2674 (7)0.4531 (7)0.4151 (7)0.0395 (10)
C70.3045 (9)0.4711 (10)0.2836 (7)0.0499 (13)
H70.28490.56560.26270.060*
C80.3715 (12)0.3449 (13)0.1842 (10)0.067 (2)
H80.40060.35590.09770.080*
C90.3935 (9)0.2066 (10)0.2156 (9)0.0587 (18)
H90.43650.12080.14980.070*
C100.3524 (9)0.1931 (9)0.3444 (10)0.0556 (16)
H100.36940.09760.36480.067*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.0618 (2)0.0660 (2)0.0781 (3)0.02555 (14)0.02487 (14)0.04774 (18)
Cl10.0653 (11)0.0710 (11)0.0816 (13)0.0210 (9)0.0091 (9)0.0445 (10)
Cl20.0623 (9)0.0551 (8)0.0628 (9)0.0170 (7)0.0277 (7)0.0314 (7)
N10.051 (3)0.058 (3)0.050 (3)0.019 (2)0.014 (2)0.027 (2)
N20.059 (3)0.043 (2)0.045 (3)0.016 (2)0.015 (2)0.024 (2)
N30.043 (2)0.041 (2)0.056 (3)0.006 (2)0.013 (2)0.023 (2)
C10.072 (5)0.078 (5)0.051 (4)0.020 (4)0.017 (3)0.033 (4)
C20.071 (5)0.084 (6)0.047 (4)0.019 (4)0.012 (3)0.017 (4)
C30.066 (4)0.061 (4)0.052 (4)0.013 (4)0.015 (3)0.009 (3)
C40.053 (3)0.045 (3)0.052 (3)0.007 (3)0.008 (3)0.014 (3)
C50.035 (2)0.043 (3)0.043 (3)0.006 (2)0.007 (2)0.019 (2)
C60.037 (2)0.040 (3)0.042 (3)0.005 (2)0.008 (2)0.017 (2)
C70.052 (3)0.060 (4)0.046 (3)0.017 (3)0.015 (2)0.026 (3)
C80.064 (4)0.088 (6)0.057 (4)0.013 (4)0.025 (3)0.032 (4)
C90.045 (3)0.054 (4)0.063 (4)0.008 (3)0.018 (3)0.003 (3)
C100.049 (3)0.047 (3)0.072 (4)0.011 (3)0.020 (3)0.021 (3)
Geometric parameters (Å, °) top
Cl1—Hg12.3875 (19)C5—N11.323 (8)
Cl2—Hg12.4579 (19)C5—N21.381 (8)
N1—Hg12.369 (6)C6—N31.341 (8)
N2—H2B0.95 (14)C6—N21.383 (8)
N3—Hg12.290 (6)C6—C71.398 (9)
C1—N11.349 (10)C7—C81.397 (11)
C1—C21.363 (13)C7—H70.9300
C1—H10.9300C8—C91.352 (14)
C2—C31.390 (14)C8—H80.9300
C2—H20.9300C9—C101.369 (12)
C3—C41.372 (11)C9—H90.9300
C3—H30.9300C10—N31.362 (9)
C4—C51.399 (9)C10—H100.9300
C4—H40.9300
N1—Hg1—Cl1112.30 (15)N2—C6—C7116.6 (5)
N1—Hg1—Cl294.92 (15)C8—C7—C6119.0 (7)
N3—Hg1—Cl1112.21 (15)C8—C7—H7120.5
N3—Hg1—Cl2123.92 (14)C6—C7—H7120.5
N3—Hg1—N182.4 (2)C9—C8—C7119.0 (7)
Cl1—Hg1—Cl2120.14 (7)C9—C8—H8120.6
N1—C1—C2123.8 (8)C7—C8—H8120.4
N1—C1—H1118.1C8—C9—C10119.9 (7)
C2—C1—H1118.1C8—C9—H9120.0
C1—C2—C3117.9 (8)C10—C9—H9120.1
C1—C2—H2121.0N3—C10—C9122.5 (7)
C3—C2—H2121.0N3—C10—H10118.7
C4—C3—C2118.7 (8)C9—C10—H10118.8
C4—C3—H3120.6C5—N1—C1118.4 (7)
C2—C3—H3120.7C5—N1—Hg1125.5 (4)
C3—C4—C5119.9 (7)C1—N1—Hg1115.7 (5)
C3—C4—H4120.1C6—N2—C5136.0 (5)
C5—C4—H4120.0C6—N2—H2B109 (8)
N1—C5—N2122.3 (6)C5—N2—H2B115 (8)
N1—C5—C4121.1 (6)C6—N3—C10118.2 (6)
N2—C5—C4116.6 (6)C6—N3—Hg1127.3 (4)
N3—C6—N2122.1 (6)C10—N3—Hg1114.4 (5)
N3—C6—C7121.3 (6)
C1—N1—Hg1—N3−169.7 (6)C6—C7—C8—C92.0 (12)
C5—N1—Hg1—N317.3 (5)C7—C8—C9—C10−0.9 (13)
C1—N1—Hg1—Cl1−58.7 (6)C8—C9—C10—N30.6 (12)
C1—N1—Hg1—Cl266.7 (6)N2—C5—N1—C1179.1 (7)
C5—N1—Hg1—Cl1128.2 (5)C4—C5—N1—C1−2.6 (10)
C5—N1—Hg1—Cl2−106.3 (5)N2—C5—N1—Hg1−8.1 (9)
C6—N3—Hg1—N1−15.5 (5)C4—C5—N1—Hg1170.3 (5)
C10—N3—Hg1—N1168.0 (5)C2—C1—N1—C51.9 (13)
C6—N3—Hg1—Cl1−126.5 (5)C2—C1—N1—Hg1−171.6 (7)
C10—N3—Hg1—Cl157.0 (5)N3—C6—N2—C517.7 (11)
C6—N3—Hg1—Cl275.3 (5)C7—C6—N2—C5−164.1 (7)
C10—N3—Hg1—Cl2−101.2 (5)N1—C5—N2—C6−15.3 (11)
N1—C1—C2—C3−1.4 (15)C4—C5—N2—C6166.3 (7)
C1—C2—C3—C41.5 (14)N2—C6—N3—C10−179.2 (6)
C2—C3—C4—C5−2.3 (12)C7—C6—N3—C102.7 (9)
C3—C4—C5—N12.8 (10)N2—C6—N3—Hg14.5 (8)
C3—C4—C5—N2−178.7 (7)C7—C6—N3—Hg1−173.7 (5)
N3—C6—C7—C8−3.0 (10)C9—C10—N3—C6−1.5 (10)
N2—C6—C7—C8178.7 (7)C9—C10—N3—Hg1175.3 (6)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···Cl2i0.95 (16)2.41 (16)3.345 (6)169 (13)
Symmetry codes: (i) −x, −y+1, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Cl1—Hg12.3875 (19)N1—Hg12.369 (6)
Cl2—Hg12.4579 (19)N3—Hg12.290 (6)
N1—Hg1—Cl1112.30 (15)N3—Hg1—Cl2123.92 (14)
N1—Hg1—Cl294.92 (15)N3—Hg1—N182.4 (2)
N3—Hg1—Cl1112.21 (15)Cl1—Hg1—Cl2120.14 (7)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N2—H2B···Cl2i0.95 (16)2.41 (16)3.345 (6)169 (13)
Symmetry codes: (i) −x, −y+1, −z+1.
Acknowledgements top

We are grateful to the Islamic Azad University, Shahr-e-Rey Branch, for financial support.

references
References top

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