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Acta Crystallogr Sect E Struct Rep Online. 2010 October 1; 66(Pt 10): m1251.
Published online 2010 September 11. doi:  10.1107/S1600536810035889
PMCID: PMC2983418

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

Abstract

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 π–π 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 [triangle]). For electroluminescent devices, see: Fan et al. (2009 [triangle]). For the crystal structures and luminescence of related Hg complexes, see: Kim et al. (2008 [triangle], 2010 [triangle]); Seo et al. (2009a [triangle],b [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-m1251-scheme1.jpg

Experimental

Crystal data

  • [HgCl2(C13H12N2)]
  • M r = 467.74
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-m1251-efi1.jpg
  • 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 [triangle]) T min = 0.094, T max = 0.118
  • 14227 measured reflections
  • 3432 independent reflections
  • 2797 reflections with I > 2σ(I)
  • R int = 0.026

Refinement

  • R[F 2 > 2σ(F 2)] = 0.026
  • wR(F 2) = 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 [triangle]); cell refinement: SAINT (Bruker, 2002 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 [triangle]) and DIAMOND (Brandenburg, 2010 [triangle]); software used to prepare material for publication: WinGX (Farrugia, 1999 [triangle]).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810035889/cv2760sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810035889/cv2760Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

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

supplementary crystallographic information

Comment

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.

Experimental

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

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.

Figures

Fig. 1.
Molecular structure of (I), showing the atom-numbering scheme and 30% probability displacement ellipsoids.
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).

Crystal data

[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

Bruker SMART CCD area-detector diffractometer2797 reflections with I > 2σ(I)
[var phi] and ω scansRint = 0.026
Absorption correction: multi-scan (SADABS; Bruker, 2002)θmax = 28.3°, θmin = 2.2°
Tmin = 0.094, Tmax = 0.118h = −11→11
14227 measured reflectionsk = −15→15
3432 independent reflectionsl = −18→18

Refinement

Refinement on F20 restraints
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.026w = 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

Special details

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)

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)
H9A−0.08390.17990.18280.052*
H9B−0.02580.17170.29110.052*
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)
H120.2082−0.09170.03920.062*
C130.2707 (6)−0.1275 (3)0.1754 (4)0.0520 (10)
H130.3261−0.19370.1640.062*
C140.2598 (5)−0.0905 (4)0.2664 (3)0.0517 (10)
H140.3086−0.13120.31710.062*
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)
Cl2−0.10125 (14)0.35992 (11)−0.00837 (8)0.0607 (3)

Atomic displacement parameters (Å2)

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, °)

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 codes: (i) −x+1, y+1/2, −z+1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: CV2760).

References

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