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access[Bis(2-pyridylmethyl)amine]dichloridomercury(II)
aDepartment of Chemistry Education and Center for Plastic Information Systems, Pusan National University, Pusan 609-735, Republic of Korea, bDepartment of Chemistry, Chungnam National University, Daejeon 305-764, Republic of Korea, cDepartment of Chemistry, Pusan National University, Pusan 609-735, Republic of Korea, and dInterdisciplinary Program of Advanced Materials for Information and Display, Pusan National University, Pusan 609-735, Republic of Korea
*Correspondence e-mail: skkang@cnu.ac.kr
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).
Related literature
For general background, see: Ojida et al. (2004![[Ojida, A., Miti-oka, Y., Sada, K. & Hamachi, I. (2004). J. Am. Chem. Soc. 126, 2454-2463.]](../../../../../../logos/arrows/e_arr.gif "Ojida, A., Miti-oka, Y., Sada, K. & Hamachi, I. (2004). J. Am. Chem. Soc. 126, 2454-2463.")
); 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).
![[Scheme 1]](tk2241scheme1.gif)
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2002); cell SAINT (Bruker, 2002); data reduction: SAINT; 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).
Supporting information
contains datablocks global, I. DOI: 10.1107/S1600536808000858/tk2241sup1.cif
Structure factors: contains datablock I. DOI: 10.1107/S1600536808000858/tk2241Isup2.hkl
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).
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 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.
Data collection: SMART (Bruker, 2002); cell 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).
![[Figure 1]](./tk2241fig1thm.gif) | 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. |
| [HgCl2(C12H13N3)] | F(000) = 880 |
| Mr = 470.74 | Dx = 2.172 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 4387 reflections |
| a = 8.4083 (6) Å | θ = 2.2–24.5° |
| b = 12.8278 (11) Å | µ = 11.05 mm−1 |
| c = 13.3457 (12) Å | T = 295 K |
| β = 90.462 (2)° | Block, orange |
| V = 1439.4 (2) Å3 | 0.18 × 0.15 × 0.15 mm |
| Z = 4 |
| Bruker SMART CCD area-detector diffractometer | 2547 reflections with I > 2σ(I) |
| ϕ and ω scans | Rint = 0.028 |
| Absorption correction: multi-scan (SADABS; Bruker, 2002) | θmax = 28.3°, θmin = 2.2° |
| Tmin = 0.143, Tmax = 0.185 | h = −11→11 |
| 15603 measured reflections | k = −12→17 |
| 3580 independent reflections | l = −17→17 |
| Refinement on F2 | 0 restraints |
| Least-squares matrix: full | H-atom parameters constrained |
| R[F2 > 2σ(F2)] = 0.027 | w = 1/[σ2(Fo2) + (0.0268P)2 + 0.7364P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.061 | (Δ/σ)max = 0.002 |
| S = 1.02 | Δρmax = 1.22 e Å−3 |
| 3580 reflections | Δρmin = −0.47 e Å−3 |
| 173 parameters |
| [HgCl2(C12H13N3)] | V = 1439.4 (2) Å3 |
| Mr = 470.74 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 8.4083 (6) Å | µ = 11.05 mm−1 |
| b = 12.8278 (11) Å | T = 295 K |
| c = 13.3457 (12) Å | 0.18 × 0.15 × 0.15 mm |
| β = 90.462 (2)° |
| 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 = 0.185 | Rint = 0.028 |
| 15603 measured reflections |
| R[F2 > 2σ(F2)] = 0.027 | 0 restraints |
| wR(F2) = 0.061 | H-atom parameters constrained |
| S = 1.02 | Δρmax = 1.22 e Å−3 |
| 3580 reflections | Δρmin = −0.47 e Å−3 |
| 173 parameters |
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. |
| x | y | z | Uiso*/Ueq | Occ. (<1) | |
| Hg | 0.87912 (2) | 0.305769 (14) | 0.873548 (12) | 0.06174 (8) | |
| Cl1 | 1.04268 (15) | 0.36276 (12) | 0.73426 (9) | 0.0791 (3) | |
| Cl2 | 0.63148 (16) | 0.21091 (10) | 0.83674 (11) | 0.0794 (4) | |
| N1 | 1.0536 (5) | 0.1777 (3) | 0.9449 (3) | 0.0636 (10) | |
| C2 | 1.1638 (6) | 0.1270 (4) | 0.8923 (4) | 0.0799 (14) | |
| H2 | 1.1708 | 0.1399 | 0.8239 | 0.096* | |
| C3 | 1.2665 (7) | 0.0573 (5) | 0.9348 (5) | 0.0911 (17) | |
| H3 | 1.3425 | 0.0235 | 0.8963 | 0.109* | |
| C4 | 1.2548 (7) | 0.0381 (5) | 1.0354 (6) | 0.0959 (18) | |
| H4 | 1.3227 | −0.0093 | 1.0665 | 0.115* | |
| C5 | 1.1423 (6) | 0.0898 (4) | 1.0893 (4) | 0.0792 (14) | |
| H5 | 1.1332 | 0.0779 | 1.1578 | 0.095* | |
| C6 | 1.0426 (5) | 0.1592 (3) | 1.0422 (3) | 0.0576 (10) | |
| C7 | 0.9172 (6) | 0.2192 (4) | 1.0981 (4) | 0.0727 (13) | |
| H7A | 0.815 | 0.1847 | 1.0914 | 0.087* | |
| H7B | 0.9447 | 0.2228 | 1.1688 | 0.087* | |
| N8 | 0.9085 (9) | 0.3260 (5) | 1.0549 (3) | 0.0594 (19) | 0.794 (14) |
| H8 | 1.0033 | 0.358 | 1.0671 | 0.071* | 0.794 (14) |
| N8A | 0.807 (3) | 0.2914 (15) | 1.0593 (11) | 0.048 (7) | 0.206 (14) |
| H8A | 0.7101 | 0.2599 | 1.0615 | 0.057* | 0.206 (14) |
| C9 | 0.7863 (6) | 0.3898 (4) | 1.0952 (3) | 0.0746 (14) | |
| H9A | 0.8204 | 0.4161 | 1.1601 | 0.09* | |
| H9B | 0.6918 | 0.3478 | 1.1053 | 0.09* | |
| C10 | 0.7454 (5) | 0.4802 (4) | 1.0282 (3) | 0.0590 (11) | |
| C11 | 0.6733 (5) | 0.5697 (4) | 1.0649 (4) | 0.0707 (13) | |
| H11 | 0.6523 | 0.5763 | 1.1329 | 0.085* | |
| C12 | 0.6337 (6) | 0.6482 (4) | 0.9995 (4) | 0.0766 (14) | |
| H12 | 0.5842 | 0.7081 | 1.0229 | 0.092* | |
| C13 | 0.6666 (6) | 0.6383 (4) | 0.9010 (4) | 0.0742 (13) | |
| H13 | 0.6408 | 0.6912 | 0.856 | 0.089* | |
| C14 | 0.7391 (5) | 0.5482 (4) | 0.8685 (3) | 0.0669 (12) | |
| H14 | 0.7622 | 0.5413 | 0.8007 | 0.08* | |
| N15 | 0.7774 (4) | 0.4704 (3) | 0.9307 (2) | 0.0563 (8) |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Hg | 0.07430 (13) | 0.06556 (13) | 0.04548 (10) | 0.01047 (9) | 0.00744 (7) | 0.00080 (8) |
| Cl1 | 0.0815 (8) | 0.0984 (10) | 0.0575 (6) | −0.0078 (7) | 0.0157 (6) | 0.0109 (6) |
| Cl2 | 0.0726 (8) | 0.0803 (9) | 0.0857 (9) | −0.0067 (6) | 0.0138 (6) | −0.0032 (6) |
| N1 | 0.061 (2) | 0.064 (2) | 0.066 (2) | 0.0019 (18) | 0.0042 (18) | 0.0070 (18) |
| C2 | 0.078 (3) | 0.077 (4) | 0.085 (3) | 0.010 (3) | 0.020 (3) | −0.004 (3) |
| C3 | 0.074 (4) | 0.069 (4) | 0.130 (5) | 0.010 (3) | 0.010 (3) | −0.020 (4) |
| C4 | 0.075 (4) | 0.072 (4) | 0.140 (6) | 0.014 (3) | −0.019 (4) | 0.006 (4) |
| C5 | 0.077 (3) | 0.076 (3) | 0.084 (3) | 0.000 (3) | −0.009 (3) | 0.017 (3) |
| C6 | 0.056 (3) | 0.053 (2) | 0.064 (3) | −0.007 (2) | −0.004 (2) | 0.008 (2) |
| C7 | 0.073 (3) | 0.086 (4) | 0.059 (3) | 0.001 (3) | 0.000 (2) | 0.017 (3) |
| N8 | 0.051 (4) | 0.067 (4) | 0.060 (3) | −0.003 (3) | 0.004 (2) | 0.003 (2) |
| N8A | 0.046 (14) | 0.053 (12) | 0.045 (9) | −0.007 (9) | −0.002 (7) | 0.009 (7) |
| C9 | 0.089 (4) | 0.082 (4) | 0.053 (3) | 0.000 (3) | 0.011 (2) | −0.003 (2) |
| C10 | 0.058 (3) | 0.063 (3) | 0.056 (2) | −0.009 (2) | 0.0045 (19) | −0.012 (2) |
| C11 | 0.068 (3) | 0.076 (3) | 0.068 (3) | −0.005 (3) | 0.010 (2) | −0.022 (3) |
| C12 | 0.058 (3) | 0.062 (3) | 0.109 (4) | 0.002 (2) | −0.001 (3) | −0.021 (3) |
| C13 | 0.068 (3) | 0.064 (3) | 0.090 (4) | −0.003 (3) | −0.003 (3) | 0.003 (3) |
| C14 | 0.074 (3) | 0.061 (3) | 0.066 (3) | −0.006 (2) | 0.006 (2) | −0.001 (2) |
| N15 | 0.060 (2) | 0.058 (2) | 0.0507 (19) | −0.0047 (17) | 0.0061 (16) | −0.0016 (16) |
| Hg—Cl1 | 2.4336 (12) | C7—H7A | 0.97 |
| Hg—Cl2 | 2.4579 (14) | C7—H7B | 0.97 |
| Hg—N1 | 2.394 (4) | N8—C9 | 1.423 (7) |
| Hg—N8 | 2.445 (5) | N8—H8 | 0.91 |
| Hg—N15 | 2.405 (4) | N8A—C9 | 1.362 (18) |
| Hg—N8A | 2.563 (17) | N8A—H8A | 0.91 |
| N1—C6 | 1.325 (6) | C9—C10 | 1.503 (7) |
| N1—C2 | 1.336 (6) | C9—H9A | 0.97 |
| C2—C3 | 1.364 (7) | C9—H9B | 0.97 |
| C2—H2 | 0.93 | C10—N15 | 1.336 (5) |
| C3—C4 | 1.370 (8) | C10—C11 | 1.389 (6) |
| C3—H3 | 0.93 | C11—C12 | 1.372 (7) |
| C4—C5 | 1.365 (8) | C11—H11 | 0.93 |
| C4—H4 | 0.93 | C12—C13 | 1.351 (7) |
| C5—C6 | 1.372 (6) | C12—H12 | 0.93 |
| C5—H5 | 0.93 | C13—C14 | 1.379 (7) |
| C6—C7 | 1.508 (7) | C13—H13 | 0.93 |
| C7—N8A | 1.407 (18) | C14—N15 | 1.337 (6) |
| C7—N8 | 1.488 (7) | C14—H14 | 0.93 |
| Cl1—Hg—Cl2 | 118.63 (5) | H7A—C7—H7B | 108.4 |
| N1—Hg—N8 | 67.82 (15) | C9—N8—C7 | 114.6 (5) |
| N1—Hg—N15 | 133.99 (12) | C9—N8—Hg | 111.6 (3) |
| N8—Hg—N15 | 68.04 (14) | C7—N8—Hg | 106.9 (3) |
| N1—Hg—Cl1 | 99.30 (10) | C9—N8—H8 | 107.8 |
| N15—Hg—Cl1 | 100.55 (9) | C7—N8—H8 | 107.8 |
| Cl1—Hg—N8 | 132.16 (19) | Hg—N8—H8 | 107.8 |
| N1—Hg—Cl2 | 104.77 (10) | C9—N8A—C7 | 124.5 (15) |
| N15—Hg—Cl2 | 101.26 (9) | C9—N8A—Hg | 107.8 (10) |
| N8—Hg—Cl2 | 109.21 (19) | C7—N8A—Hg | 104.1 (10) |
| N1—Hg—N8A | 73.5 (4) | C9—N8A—H8A | 106.4 |
| N15—Hg—N8A | 70.7 (4) | C7—N8A—H8A | 106.4 |
| Cl1—Hg—N8A | 154.1 (6) | Hg—N8A—H8A | 106.4 |
| N8—Hg—N8A | 22.0 (5) | N8A—C9—C10 | 122.3 (7) |
| Cl2—Hg—N8A | 87.2 (6) | N8—C9—C10 | 112.4 (4) |
| C6—N1—C2 | 118.8 (4) | N8A—C9—H9A | 126.8 |
| C6—N1—Hg | 117.8 (3) | N8—C9—H9A | 109.1 |
| C2—N1—Hg | 123.4 (3) | C10—C9—H9A | 109.1 |
| N1—C2—C3 | 122.7 (5) | N8—C9—H9B | 109.1 |
| N1—C2—H2 | 118.6 | C10—C9—H9B | 109.1 |
| C3—C2—H2 | 118.6 | H9A—C9—H9B | 107.9 |
| C2—C3—C4 | 118.4 (5) | N15—C10—C11 | 120.9 (5) |
| C2—C3—H3 | 120.8 | N15—C10—C9 | 117.4 (4) |
| C4—C3—H3 | 120.8 | C11—C10—C9 | 121.7 (4) |
| C5—C4—C3 | 119.1 (5) | C12—C11—C10 | 119.1 (5) |
| C5—C4—H4 | 120.5 | C12—C11—H11 | 120.5 |
| C3—C4—H4 | 120.5 | C10—C11—H11 | 120.5 |
| C4—C5—C6 | 119.8 (5) | C13—C12—C11 | 120.0 (5) |
| C4—C5—H5 | 120.1 | C13—C12—H12 | 120 |
| C6—C5—H5 | 120.1 | C11—C12—H12 | 120 |
| N1—C6—C5 | 121.3 (5) | C12—C13—C14 | 118.6 (5) |
| N1—C6—C7 | 116.6 (4) | C12—C13—H13 | 120.7 |
| C5—C6—C7 | 122.1 (4) | C14—C13—H13 | 120.7 |
| N8A—C7—C6 | 127.9 (8) | N15—C14—C13 | 122.4 (4) |
| N8—C7—C6 | 108.1 (4) | N15—C14—H14 | 118.8 |
| N8—C7—H7A | 110.1 | C13—C14—H14 | 118.8 |
| C6—C7—H7A | 110.1 | C10—N15—C14 | 119.0 (4) |
| N8A—C7—H7B | 118.6 | C10—N15—Hg | 117.8 (3) |
| N8—C7—H7B | 110.1 | C14—N15—Hg | 122.9 (3) |
| C6—C7—H7B | 110.1 |
Experimental details
| Crystal data | |
| Chemical formula | [HgCl2(C12H13N3)] |
| Mr | 470.74 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 295 |
| a, b, c (Å) | 8.4083 (6), 12.8278 (11), 13.3457 (12) |
| β (°) | 90.462 (2) |
| V (Å3) | 1439.4 (2) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 11.05 |
| Crystal size (mm) | 0.18 × 0.15 × 0.15 |
| Data collection | |
| Diffractometer | Bruker SMART CCD area-detector diffractometer |
| Absorption correction | Multi-scan (SADABS; Bruker, 2002) |
| Tmin, Tmax | 0.143, 0.185 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 15603, 3580, 2547 |
| Rint | 0.028 |
| (sin θ/λ)max (Å−1) | 0.667 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.027, 0.061, 1.02 |
| No. of reflections | 3580 |
| No. of parameters | 173 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 1.22, −0.47 |
Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).
| Hg—Cl1 | 2.4336 (12) | Hg—N8 | 2.445 (5) |
| Hg—Cl2 | 2.4579 (14) | Hg—N15 | 2.405 (4) |
| Hg—N1 | 2.394 (4) | ||
| Cl1—Hg—Cl2 | 118.63 (5) | N1—Hg—N15 | 133.99 (12) |
| N1—Hg—N8 | 67.82 (15) | N8—Hg—N15 | 68.04 (14) |
Acknowledgements
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
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
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.