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ISSN: 2056-9890

[Benz­yl(2-pyridyl­methyl­­idene)amine]­di­chloridomercury(II)

aDepartment of Chemistry Education and Interdisciplinary Program of Advanced Information and Display Materials, Pusan National University, Busan 609-735, Republic of Korea, and bDepartment of Chemistry, Chungnam National University, Daejeon 305-764, Republic of Korea
*Correspondence e-mail: skkang@cnu.ac.kr

(Received 2 September 2010; accepted 7 September 2010; online 11 September 2010)

The HgII ion in the title complex, [HgCl2(C13H12N2)], adopts a distorted tetra­hedral geometry being coordinated by two Cl anions and by two N atoms of the benz­yl(2-pyridyl­methyl­ene)amine ligand. The Cl—Hg—Cl plane is twisted at 70.1 (1)° from the mean plane of the chelate ring. In the crystal structure, inter­molecular ππ inter­actions [centroid–centroid distance = 3.793 (3) Å] between the aromatic rings link the mol­ecules into zigzag chains extending along [010].

Related literature

For chemosensors of mercury ions, see: Zhou et al. (2010[Zhou, Y., Zhu, C.-Y., Gao, X.-S., You, X.-Y. & Yao, C. (2010). Org. Lett. 12, 2566-2569.]). For electroluminescent devices, see: Fan et al. (2009[Fan, B., Yang, Y., Yin, Y., Hasi, W. & Mu, Y. (2009). Inorg. Chem. 48, 6034-6043.]). For the crystal structures and luminescence of related Hg complexes, see: Kim et al. (2008[Kim, Y.-I., Lee, Y.-S., Seo, H.-J., Nam, K.-S. & Kang, S. K. (2008). Acta Cryst. E64, m358.], 2010[Kim, Y.-I., Seo, H.-J., Kim, J.-H., Lee, Y.-S. & Kang, S. K. (2010). Acta Cryst. E66, m124.]); Seo et al. (2009a[Seo, H.-J., Kim, Y.-I., Lee, Y.-S. & Kang, S. K. (2009a). Acta Cryst. E65, m55.],b[Seo, H.-J., Ryu, J. S., Nam, K.-S., Kang, S. K., Park, S. Y. & Kim, Y.-I. (2009b). Bull. Korean Chem. Soc. 30, 3109-3112.]).

[Scheme 1]

Experimental

Crystal data
  • [HgCl2(C13H12N2)]

  • Mr = 467.74

  • Monoclinic, P 21 /c

  • a = 8.2736 (1) Å

  • b = 11.8828 (2) Å

  • c = 14.1191 (2) Å

  • β = 94.343 (1)°

  • V = 1384.11 (3) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 11.49 mm−1

  • T = 295 K

  • 0.22 × 0.20 × 0.18 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2002[Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.094, Tmax = 0.118

  • 14227 measured reflections

  • 3432 independent reflections

  • 2797 reflections with I > 2σ(I)

  • Rint = 0.026

Refinement
  • R[F2 > 2σ(F2)] = 0.026

  • wR(F2) = 0.056

  • S = 1.03

  • 3432 reflections

  • 163 parameters

  • H-atom parameters constrained

  • Δρmax = 1.03 e Å−3

  • Δρmin = −1.61 e Å−3

Data collection: SMART (Bruker, 2002[Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2002[Bruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997[Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.]) and DIAMOND (Brandenburg, 2010[Brandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany.]); software used to prepare material for publication: WinGX (Farrugia, 1999[Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837-838.]).

Supporting information


Comment top

Luminescent mercury(II) compounds with nitrogen-containing ligands have reported in studies concerning their performance in chemosensors for mercury ions (Zhou et al., 2010) and electroluminescent devices (Fan et al., 2009). As an extension of our work (Kim et al., 2010; Seo et al., 2009a, b; Kim et al., 2008) on luminescent mercury(II) complexes, herein, we report here the crystal structure and luminescent properties of the title HgII chloride complex with benzyl(2-pyridylmethylene)amine (bpma), (I).

In (I) (Fig. 1), the HgII ion is coordinated by two N atoms of bpma ligand and two Cl anions. The angles around Hg atom are in the range of 71.00 (10) – 136.35 (8)°, suggesting the coordination geometry around the Hg atom is described as a distorted tetrahedron. The Cl—Hg—Cl plane is twisted at 70.1 (1)° from the mean plane of the chelate ring. The phenyl ring on the bpma ligand is twisted out of the pyridine plane, and form a dihedral angel of 67.9 (1)°. In the crystal structure, there are weak π-π interactions between the aromatic rings of the discrete units (Table 1), which link the molecules into zigzag chains extended in direction [010] (Fig. 2).

The title complex exhibited an emission (λmax,PL = 426 nm in DMF) upon 280 nm excitation with the quantum yield of 2.9%, which was contributed from the intra-ligand (IL) 1(π-π*) transition.

Related literature top

For chemosensors of mercury ions, see: Zhou et al. (2010). For electroluminescent devices, see: Fan et al. (2009). For the crystal structures and luminescence of related Hg complexes, see: Kim et al. (2008, 2010); Seo et al. (2009a,b).

Experimental top

All of the reagents and solvents were commercially purchased from Aldrich and used without further purification. Benzyl(2-pyridylmethylene)amine (bpma) was synthesized from the reaction of 2-pyridinecarboxylaldehyde and benzylamine. A solution of benzylamine (20 mmol) in methanol (30 ml) was added to a solution of 2-pyridinecarboxylaldehyde (20 mmol) in methanol (30 ml), and the mixture was stirred for 3 h at room temperature. To a stirred solution of bpma was added mercuric chloride (20 mmol) in methanol (30 ml). The solution was stirred for 6 h at room temperature. The white crystals were obtained after recrystallization from methanol solution.

Refinement top

All H atoms were positioned geometrically and refined using a riding model, with C—H = 0.93 - 0.97 Å, and with Uiso(H) = 1.2Ueq(C). The maximal residual peak and minimal residual hole situated at 0.78 and 0.79 Å, respectively, from the Hg1 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) and DIAMOND (Brandenburg, 2010); 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 displacement ellipsoids.
[Figure 2] Fig. 2. A portion of the crystal packing showing zigzag chain (extended in direction [010]) of the molecules linked by π-π interactions (dotted lines).
[Benzyl(2-pyridylmethylidene)amine]dichloridomercury(II) top
Crystal data top
[HgCl2(C13H12N2)]F(000) = 872
Mr = 467.74Dx = 2.245 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5055 reflections
a = 8.2736 (1) Åθ = 2.2–27.7°
b = 11.8828 (2) ŵ = 11.49 mm1
c = 14.1191 (2) ÅT = 295 K
β = 94.343 (1)°Block, colourless
V = 1384.11 (3) Å30.22 × 0.2 × 0.18 mm
Z = 4
Data collection top
Bruker SMART CCD area-detector
diffractometer
2797 reflections with I > 2σ(I)
ϕ and ω scansRint = 0.026
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
θmax = 28.3°, θmin = 2.2°
Tmin = 0.094, Tmax = 0.118h = 1111
14227 measured reflectionsk = 1515
3432 independent reflectionsl = 1818
Refinement top
Refinement on F20 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.026 w = 1/[σ2(Fo2) + (0.0212P)2 + 1.9423P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.056(Δ/σ)max = 0.001
S = 1.03Δρmax = 1.03 e Å3
3432 reflectionsΔρmin = 1.61 e Å3
163 parameters
Crystal data top
[HgCl2(C13H12N2)]V = 1384.11 (3) Å3
Mr = 467.74Z = 4
Monoclinic, P21/cMo Kα radiation
a = 8.2736 (1) ŵ = 11.49 mm1
b = 11.8828 (2) ÅT = 295 K
c = 14.1191 (2) Å0.22 × 0.2 × 0.18 mm
β = 94.343 (1)°
Data collection top
Bruker SMART CCD area-detector
diffractometer
3432 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2002)
2797 reflections with I > 2σ(I)
Tmin = 0.094, Tmax = 0.118Rint = 0.026
14227 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0260 restraints
wR(F2) = 0.056H-atom parameters constrained
S = 1.03Δρmax = 1.03 e Å3
3432 reflectionsΔρmin = 1.61 e Å3
163 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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Hg10.16420 (2)0.368809 (15)0.072427 (10)0.04946 (7)
N10.2879 (3)0.4688 (2)0.1992 (2)0.0354 (7)
C20.3837 (5)0.5579 (3)0.1919 (3)0.0457 (9)
H20.40390.58420.13190.055*
C30.4543 (5)0.6126 (3)0.2713 (4)0.0561 (12)
H30.51910.67560.26450.067*
C40.4283 (5)0.5735 (4)0.3594 (4)0.0539 (11)
H40.4740.60960.41330.065*
C50.3333 (5)0.4797 (4)0.3671 (3)0.0471 (10)
H50.31570.45060.42660.056*
C60.2642 (4)0.4290 (3)0.2860 (2)0.0341 (7)
C70.1618 (4)0.3282 (3)0.2917 (3)0.0353 (8)
H70.13240.30390.35070.042*
N80.1135 (4)0.2744 (2)0.2183 (2)0.0350 (6)
C90.0108 (5)0.1746 (3)0.2275 (3)0.0430 (9)
H9A0.08390.17990.18280.052*
H9B0.02580.17170.29110.052*
C100.1029 (4)0.0685 (3)0.2085 (3)0.0356 (8)
C110.1158 (5)0.0304 (3)0.1168 (3)0.0441 (9)
H110.06780.07070.06570.053*
C120.1996 (5)0.0669 (4)0.1011 (3)0.0519 (10)
H120.20820.09170.03920.062*
C130.2707 (6)0.1275 (3)0.1754 (4)0.0520 (10)
H130.32610.19370.1640.062*
C140.2598 (5)0.0905 (4)0.2664 (3)0.0517 (10)
H140.30860.13120.31710.062*
C150.1764 (5)0.0073 (3)0.2832 (3)0.0442 (9)
H150.16960.03230.34520.053*
Cl10.39293 (15)0.30109 (10)0.00900 (8)0.0599 (3)
Cl20.10125 (14)0.35992 (11)0.00837 (8)0.0607 (3)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.05046 (10)0.06449 (12)0.03322 (8)0.00618 (8)0.00188 (6)0.00268 (7)
N10.0322 (15)0.0313 (16)0.0423 (16)0.0000 (12)0.0001 (12)0.0043 (13)
C20.037 (2)0.037 (2)0.063 (3)0.0032 (17)0.0030 (18)0.0095 (19)
C30.034 (2)0.029 (2)0.102 (4)0.0029 (16)0.009 (2)0.003 (2)
C40.052 (2)0.042 (2)0.065 (3)0.003 (2)0.016 (2)0.014 (2)
C50.049 (2)0.046 (2)0.044 (2)0.0038 (19)0.0083 (18)0.0101 (18)
C60.0327 (17)0.0312 (18)0.0380 (18)0.0056 (15)0.0002 (14)0.0026 (15)
C70.0371 (19)0.0343 (18)0.0351 (18)0.0044 (15)0.0070 (14)0.0033 (15)
N80.0356 (15)0.0318 (16)0.0379 (16)0.0032 (13)0.0044 (12)0.0003 (13)
C90.039 (2)0.037 (2)0.055 (2)0.0078 (17)0.0115 (17)0.0017 (18)
C100.0355 (18)0.0303 (19)0.0414 (19)0.0094 (15)0.0058 (15)0.0001 (15)
C110.054 (2)0.038 (2)0.039 (2)0.0025 (18)0.0003 (17)0.0024 (17)
C120.059 (3)0.047 (2)0.050 (2)0.002 (2)0.009 (2)0.012 (2)
C130.055 (2)0.031 (2)0.072 (3)0.0005 (19)0.012 (2)0.003 (2)
C140.055 (3)0.040 (2)0.059 (3)0.005 (2)0.003 (2)0.014 (2)
C150.056 (2)0.042 (2)0.0353 (19)0.0159 (19)0.0032 (17)0.0016 (17)
Cl10.0642 (7)0.0605 (7)0.0570 (6)0.0117 (6)0.0186 (5)0.0063 (5)
Cl20.0559 (6)0.0762 (8)0.0479 (6)0.0078 (6)0.0095 (5)0.0080 (5)
Geometric parameters (Å, º) top
Hg1—N12.321 (3)C7—H70.93
Hg1—Cl22.3993 (11)N8—C91.470 (5)
Hg1—N82.409 (3)C9—C101.507 (5)
Hg1—Cl12.4249 (11)C9—H9A0.97
N1—C21.331 (5)C9—H9B0.97
N1—C61.342 (4)C10—C111.382 (5)
C2—C31.387 (6)C10—C151.384 (5)
C2—H20.93C11—C121.375 (6)
C3—C41.359 (7)C11—H110.93
C3—H30.93C12—C131.368 (6)
C4—C51.373 (6)C12—H120.93
C4—H40.93C13—C141.368 (6)
C5—C61.379 (5)C13—H130.93
C5—H50.93C14—C151.381 (6)
C6—C71.473 (5)C14—H140.93
C7—N81.258 (5)C15—H150.93
Cg1···Cg2i3.793 (3)
N1—Hg1—Cl2136.35 (8)C7—N8—C9119.1 (3)
N1—Hg1—N871.00 (10)C7—N8—Hg1113.8 (2)
Cl2—Hg1—N899.99 (8)C9—N8—Hg1126.2 (2)
N1—Hg1—Cl1102.78 (8)N8—C9—C10110.9 (3)
Cl2—Hg1—Cl1118.63 (4)N8—C9—H9A109.5
N8—Hg1—Cl1116.32 (8)C10—C9—H9A109.5
C2—N1—C6118.7 (3)N8—C9—H9B109.5
C2—N1—Hg1125.3 (3)C10—C9—H9B109.5
C6—N1—Hg1115.9 (2)H9A—C9—H9B108.1
N1—C2—C3121.8 (4)C11—C10—C15118.7 (4)
N1—C2—H2119.1C11—C10—C9121.1 (4)
C3—C2—H2119.1C15—C10—C9120.2 (3)
C4—C3—C2119.6 (4)C12—C11—C10120.2 (4)
C4—C3—H3120.2C12—C11—H11119.9
C2—C3—H3120.2C10—C11—H11119.9
C3—C4—C5118.8 (4)C13—C12—C11120.8 (4)
C3—C4—H4120.6C13—C12—H12119.6
C5—C4—H4120.6C11—C12—H12119.6
C4—C5—C6119.5 (4)C14—C13—C12119.7 (4)
C4—C5—H5120.3C14—C13—H13120.1
C6—C5—H5120.3C12—C13—H13120.1
N1—C6—C5121.6 (4)C13—C14—C15120.1 (4)
N1—C6—C7117.5 (3)C13—C14—H14120
C5—C6—C7120.9 (3)C15—C14—H14120
N8—C7—C6121.1 (3)C14—C15—C10120.5 (4)
N8—C7—H7119.5C14—C15—H15119.7
C6—C7—H7119.5C10—C15—H15119.7
Symmetry code: (i) x+1, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formula[HgCl2(C13H12N2)]
Mr467.74
Crystal system, space groupMonoclinic, P21/c
Temperature (K)295
a, b, c (Å)8.2736 (1), 11.8828 (2), 14.1191 (2)
β (°) 94.343 (1)
V3)1384.11 (3)
Z4
Radiation typeMo Kα
µ (mm1)11.49
Crystal size (mm)0.22 × 0.2 × 0.18
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 2002)
Tmin, Tmax0.094, 0.118
No. of measured, independent and
observed [I > 2σ(I)] reflections
14227, 3432, 2797
Rint0.026
(sin θ/λ)max1)0.667
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.026, 0.056, 1.03
No. of reflections3432
No. of parameters163
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)1.03, 1.61

Computer programs: SMART (Bruker, 2002), SAINT (Bruker, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and DIAMOND (Brandenburg, 2010), WinGX (Farrugia, 1999).

 

Acknowledgements

This work was supported by a Korea Research Foundation Grant funded by the Korean government (MOEHRD) (KRF-2006–521-C00083).

References

First citationBrandenburg, K. (2010). DIAMOND. Crystal Impact GbR, Bonn, Germany.  Google Scholar
First citationBruker (2002). SADABS, SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFan, B., Yang, Y., Yin, Y., Hasi, W. & Mu, Y. (2009). Inorg. Chem. 48, 6034–6043.  Web of Science CSD CrossRef PubMed CAS Google Scholar
First citationFarrugia, L. J. (1997). J. Appl. Cryst. 30, 565.  CrossRef IUCr Journals Google Scholar
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First citationSeo, H.-J., Kim, Y.-I., Lee, Y.-S. & Kang, S. K. (2009a). Acta Cryst. E65, m55.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSeo, H.-J., Ryu, J. S., Nam, K.-S., Kang, S. K., Park, S. Y. & Kim, Y.-I. (2009b). Bull. Korean Chem. Soc. 30, 3109–3112.  CrossRef CAS Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationZhou, Y., Zhu, C.-Y., Gao, X.-S., You, X.-Y. & Yao, C. (2010). Org. Lett. 12, 2566–2569.  Web of Science CrossRef CAS PubMed Google Scholar

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