supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

tk2241 scheme

Acta Cryst. (2008). E64, m358    [ doi:10.1107/S1600536808000858 ]

[Bis(2-pyridylmethyl)amine]dichloridomercury(II)

Y.-I. Kim, Y.-S. Lee, H.-J. Seo, K.-S. Nam and S. K. Kang

Abstract top

The Hg atom in the title complex, [HgCl2(C12H13N3)], adopts a square-pyramidal geometry, being ligated by three N atoms of the tridentate bis(2-pyridylmethyl)amine ligand and two Cl atoms, with one of the latter occupying the apical position. Disorder is noted in the amine portion of the ligand and this was modelled over two sites, with the major component having a site-occupancy factor of 0.794 (14).

Comment top

Transition metal complexes with bis(2-pyridylmethyl)amine (dpa) or substituted-dpa ligands continue to be of interest in many fields of chemistry (Kirin et al., 2005; Storr et al., 2005; Tamamura et al., 2006). Recently, we reported Cu(II) (Lee et al., 2007) and Zn(II) (Kim et al., 2007) halide complexes with the dpa ligand, and Zn(dpa)Cl2 was proposed as a blue fluorescent material. In this work, as an extension of a study on fluorescent chemosensors (Ojida et al., 2004), we prepared a Hg(II) complex of dpa, Hg(dpa)Cl2 (I), and its structure and properties were investigated. The Hg(II) atom is 5-coordinated by the three N atoms of the tridentate di(picolyl)amine ligand and two Cl atoms. The coordination geometry is based on a square pyramid with the basal plane defined by three N atoms and one Cl, with the other Cl atom occupying the apical position. The calculated trigonality index, τ = 0.03, indicates that the Hg atom is in a square pyramidal geometry (Addison et al., 1984). Hg(dpa)Cl2 exhibits an intense blue emission at 425 nm in DMF solution upon excitation at 400 nm.

Related literature top

For general background, see: Ojida et al. (2004); Kirin et al. (2005); Storr et al. (2005); Tamamura et al. (2006); Kim et al. (2007); Lee et al. (2007). For related literature, see: Addison et al. (1984).

Experimental top

All of the reagents and solvents were purchased from either Aldrich and used without further purification. A mixture of mercuric chloride (1.35 g, 5 mmol) and bis(2-pyridylmethyl)amine (0.99 g, 5 mmol) in methanol (20 ml) was stirred for 8 h at room temperature under a nitrogen atmosphere. The precipitates were filtered off and recrystallized from methanol in a 63% yield. 1H-NMR for dpa in (I) (d6-DMSO, p.p.m.): δ: 8.51 (d, 2H), 7.96 (t, 2H), 7.52 (m, 4H), 4.98 (s, 1H), 4.08 (s, 4H).

Refinement top

The C and N-bound H atoms were included in the riding model approximation with C—H = 0.93–0.97 Å and N—H = 0.91 Å, and with Uiso(H) = 1.2Ueq(C and N). Disorder was noted in the structure and this modelled so that two sites were resolved for the N8—H atoms. From refinement, the major component of the disorder had a site occupancy factor = 0.794 (14). The maximum and minimum residual electron denisty peaks were located 0.85 and 0.78 Å, respectively, from the Hg atom.

Computing details top

Data collection: SMART (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT (Bruker, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (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. Molecular structure of (I), showing the atom-numbering scheme and 30% probability ellipsoids. Only the major component of the disordered atoms is shown for clarity.
[Bis(2-pyridylmethyl)amine]dichloridomercury(II) top
Crystal data top
[HgCl2(C12H13N3)]F000 = 880
Mr = 470.74Dx = 2.172 Mg m−3
Monoclinic, P21/nMo Kα radiation
λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 4387 reflections
a = 8.4083 (6) Åθ = 2.2–24.5º
b = 12.8278 (11) ŵ = 11.05 mm−1
c = 13.3457 (12) ÅT = 295 (2) K
β = 90.462 (2)ºBlock, orange
V = 1439.4 (2) Å30.18 × 0.15 × 0.15 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer		Rint = 0.028
φ and ω scansθmax = 28.3º
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		θmin = 2.2º
Tmin = 0.143, Tmax = 0.185h = −11→11
15603 measured reflectionsk = −12→17
3580 independent reflectionsl = −17→17
2547 reflections with I > 2σ(I)
Refinement top
Refinement on F2H-atom parameters constrained
Least-squares matrix: full  w = 1/[σ2(Fo2) + (0.0268P)2 + 0.7364P]
where P = (Fo2 + 2Fc2)/3
R[F2 > 2σ(F2)] = 0.027(Δ/σ)max = 0.002
wR(F2) = 0.061Δρmax = 1.22 e Å−3
S = 1.02Δρmin = −0.47 e Å−3
3580 reflectionsExtinction correction: none
173 parameters
Crystal data top
[HgCl2(C12H13N3)]V = 1439.4 (2) Å3
Mr = 470.74Z = 4
Monoclinic, P21/nMo Kα
a = 8.4083 (6) ŵ = 11.05 mm−1
b = 12.8278 (11) ÅT = 295 (2) K
c = 13.3457 (12) Å0.18 × 0.15 × 0.15 mm
β = 90.462 (2)º
Data collection top
Bruker SMART CCD area-detector
diffractometer		3580 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)		2547 reflections with I > 2σ(I)
Tmin = 0.143, Tmax = 0.185Rint = 0.028
15603 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.027173 parameters
wR(F2) = 0.061H-atom parameters constrained
S = 1.02Δρmax = 1.22 e Å−3
3580 reflectionsΔρmin = −0.47 e Å−3
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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Hg0.87912 (2)0.305769 (14)0.873548 (12)0.06174 (8)
Cl11.04268 (15)0.36276 (12)0.73426 (9)0.0791 (3)
Cl20.63148 (16)0.21091 (10)0.83674 (11)0.0794 (4)
N11.0536 (5)0.1777 (3)0.9449 (3)0.0636 (10)
C21.1638 (6)0.1270 (4)0.8923 (4)0.0799 (14)
H21.17080.13990.82390.096*
C31.2665 (7)0.0573 (5)0.9348 (5)0.0911 (17)
H31.34250.02350.89630.109*
C41.2548 (7)0.0381 (5)1.0354 (6)0.0959 (18)
H41.3227−0.00931.06650.115*
C51.1423 (6)0.0898 (4)1.0893 (4)0.0792 (14)
H51.13320.07791.15780.095*
C61.0426 (5)0.1592 (3)1.0422 (3)0.0576 (10)
C70.9172 (6)0.2192 (4)1.0981 (4)0.0727 (13)
H7A0.8150.18471.09140.087*
H7B0.94470.22281.16880.087*
N80.9085 (9)0.3260 (5)1.0549 (3)0.0594 (19)0.794 (14)
H81.00330.3581.06710.071*0.794 (14)
N8A0.807 (3)0.2914 (15)1.0593 (11)0.048 (7)0.206 (14)
H8A0.71010.25991.06150.057*0.206 (14)
C90.7863 (6)0.3898 (4)1.0952 (3)0.0746 (14)
H9A0.82040.41611.16010.09*
H9B0.69180.34781.10530.09*
C100.7454 (5)0.4802 (4)1.0282 (3)0.0590 (11)
C110.6733 (5)0.5697 (4)1.0649 (4)0.0707 (13)
H110.65230.57631.13290.085*
C120.6337 (6)0.6482 (4)0.9995 (4)0.0766 (14)
H120.58420.70811.02290.092*
C130.6666 (6)0.6383 (4)0.9010 (4)0.0742 (13)
H130.64080.69120.8560.089*
C140.7391 (5)0.5482 (4)0.8685 (3)0.0669 (12)
H140.76220.54130.80070.08*
N150.7774 (4)0.4704 (3)0.9307 (2)0.0563 (8)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg0.07430 (13)0.06556 (13)0.04548 (10)0.01047 (9)0.00744 (7)0.00080 (8)
Cl10.0815 (8)0.0984 (10)0.0575 (6)−0.0078 (7)0.0157 (6)0.0109 (6)
Cl20.0726 (8)0.0803 (9)0.0857 (9)−0.0067 (6)0.0138 (6)−0.0032 (6)
N10.061 (2)0.064 (2)0.066 (2)0.0019 (18)0.0042 (18)0.0070 (18)
C20.078 (3)0.077 (4)0.085 (3)0.010 (3)0.020 (3)−0.004 (3)
C30.074 (4)0.069 (4)0.130 (5)0.010 (3)0.010 (3)−0.020 (4)
C40.075 (4)0.072 (4)0.140 (6)0.014 (3)−0.019 (4)0.006 (4)
C50.077 (3)0.076 (3)0.084 (3)0.000 (3)−0.009 (3)0.017 (3)
C60.056 (3)0.053 (2)0.064 (3)−0.007 (2)−0.004 (2)0.008 (2)
C70.073 (3)0.086 (4)0.059 (3)0.001 (3)0.000 (2)0.017 (3)
N80.051 (4)0.067 (4)0.060 (3)−0.003 (3)0.004 (2)0.003 (2)
N8A0.046 (14)0.053 (12)0.045 (9)−0.007 (9)−0.002 (7)0.009 (7)
C90.089 (4)0.082 (4)0.053 (3)0.000 (3)0.011 (2)−0.003 (2)
C100.058 (3)0.063 (3)0.056 (2)−0.009 (2)0.0045 (19)−0.012 (2)
C110.068 (3)0.076 (3)0.068 (3)−0.005 (3)0.010 (2)−0.022 (3)
C120.058 (3)0.062 (3)0.109 (4)0.002 (2)−0.001 (3)−0.021 (3)
C130.068 (3)0.064 (3)0.090 (4)−0.003 (3)−0.003 (3)0.003 (3)
C140.074 (3)0.061 (3)0.066 (3)−0.006 (2)0.006 (2)−0.001 (2)
N150.060 (2)0.058 (2)0.0507 (19)−0.0047 (17)0.0061 (16)−0.0016 (16)
Geometric parameters (Å, °) top
Hg—Cl12.4336 (12)C7—H7A0.97
Hg—Cl22.4579 (14)C7—H7B0.97
Hg—N12.394 (4)N8—C91.423 (7)
Hg—N82.445 (5)N8—H80.91
Hg—N152.405 (4)N8A—C91.362 (18)
Hg—N8A2.563 (17)N8A—H8A0.91
N1—C61.325 (6)C9—C101.503 (7)
N1—C21.336 (6)C9—H9A0.97
C2—C31.364 (7)C9—H9B0.97
C2—H20.93C10—N151.336 (5)
C3—C41.370 (8)C10—C111.389 (6)
C3—H30.93C11—C121.372 (7)
C4—C51.365 (8)C11—H110.93
C4—H40.93C12—C131.351 (7)
C5—C61.372 (6)C12—H120.93
C5—H50.93C13—C141.379 (7)
C6—C71.508 (7)C13—H130.93
C7—N8A1.407 (18)C14—N151.337 (6)
C7—N81.488 (7)C14—H140.93
Cl1—Hg—Cl2118.63 (5)H7A—C7—H7B108.4
N1—Hg—N867.82 (15)C9—N8—C7114.6 (5)
N1—Hg—N15133.99 (12)C9—N8—Hg111.6 (3)
N8—Hg—N1568.04 (14)C7—N8—Hg106.9 (3)
N1—Hg—Cl199.30 (10)C9—N8—H8107.8
N15—Hg—Cl1100.55 (9)C7—N8—H8107.8
Cl1—Hg—N8132.16 (19)Hg—N8—H8107.8
N1—Hg—Cl2104.77 (10)C9—N8A—C7124.5 (15)
N15—Hg—Cl2101.26 (9)C9—N8A—Hg107.8 (10)
N8—Hg—Cl2109.21 (19)C7—N8A—Hg104.1 (10)
N1—Hg—N8A73.5 (4)C9—N8A—H8A106.4
N15—Hg—N8A70.7 (4)C7—N8A—H8A106.4
Cl1—Hg—N8A154.1 (6)Hg—N8A—H8A106.4
N8—Hg—N8A22.0 (5)N8A—C9—C10122.3 (7)
Cl2—Hg—N8A87.2 (6)N8—C9—C10112.4 (4)
C6—N1—C2118.8 (4)N8A—C9—H9A126.8
C6—N1—Hg117.8 (3)N8—C9—H9A109.1
C2—N1—Hg123.4 (3)C10—C9—H9A109.1
N1—C2—C3122.7 (5)N8—C9—H9B109.1
N1—C2—H2118.6C10—C9—H9B109.1
C3—C2—H2118.6H9A—C9—H9B107.9
C2—C3—C4118.4 (5)N15—C10—C11120.9 (5)
C2—C3—H3120.8N15—C10—C9117.4 (4)
C4—C3—H3120.8C11—C10—C9121.7 (4)
C5—C4—C3119.1 (5)C12—C11—C10119.1 (5)
C5—C4—H4120.5C12—C11—H11120.5
C3—C4—H4120.5C10—C11—H11120.5
C4—C5—C6119.8 (5)C13—C12—C11120.0 (5)
C4—C5—H5120.1C13—C12—H12120
C6—C5—H5120.1C11—C12—H12120
N1—C6—C5121.3 (5)C12—C13—C14118.6 (5)
N1—C6—C7116.6 (4)C12—C13—H13120.7
C5—C6—C7122.1 (4)C14—C13—H13120.7
N8A—C7—C6127.9 (8)N15—C14—C13122.4 (4)
N8—C7—C6108.1 (4)N15—C14—H14118.8
N8—C7—H7A110.1C13—C14—H14118.8
C6—C7—H7A110.1C10—N15—C14119.0 (4)
N8A—C7—H7B118.6C10—N15—Hg117.8 (3)
N8—C7—H7B110.1C14—N15—Hg122.9 (3)
C6—C7—H7B110.1
Table 1
Selected geometric parameters (Å, °) top
Hg—Cl12.4336 (12)Hg—N82.445 (5)
Hg—Cl22.4579 (14)Hg—N152.405 (4)
Hg—N12.394 (4)
Cl1—Hg—Cl2118.63 (5)N1—Hg—N15133.99 (12)
N1—Hg—N867.82 (15)N8—Hg—N1568.04 (14)
Acknowledgements top

This work was supported by the Ministry of Information and Communication, Korea, under the Information Technology Research Center (ITRC) Support Program. X-ray data were collected at the Center for Research Facilities in Chungnam National University.

references
References top

Addison, A. W., Rao, T. N., Reedijk, J., van Rijn, J. & Verschoor, G. C. (1984). J. Chem. Soc. Dalton Trans. pp. 1349–1356.

Bruker (2002). SADABS (Version 2.03), SAINT (Version 6.02) and SMART (Version 5.62). Bruker AXS Inc., Madison, Wisconsin, USA.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565–?.

Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838.

Kim, Y.-I., Lee, Y.-S., Seo, H.-J., Lee, J.-Y. & Kang, S. K. (2007). Acta Cryst. E63, m2810–m2811.

Kirin, S. I., Dübon, P., Weyhermüller, T., Bill, E. & Metgler-Nolte, N. (2005). Inorg. Chem. 44, 5405–5415.

Lee, H.-W., Seo, H.-J., Kim, H.-J., Kang, S. K., Heo, J. Y. & Kim, Y.-I. (2007). Bull. Korean Chem. Soc. 28, 855–858.

Ojida, A., Miti-oka, Y., Sada, K. & Hamachi, I. (2004). J. Am. Chem. Soc. 126, 2454–2463.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Storr, T., Sugai, Y., Borta, C. A., Mikata, Y., Adam, M. J., Yano, S. & Orvig, C. (2005). Inorg. Chem. 44, 2698–2705.

Tamamura, H., Ojida, A., Ogawa, T., Tsutsumi, H., Masuno, H., Nakashima, H., Yamamoto, N., Hamachi, I. & Fujii, N. (2006). J. Med. Chem. 49, 3412–3415.