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Acta Cryst. (2007). E63, m2074    [ doi:10.1107/S1600536807032047 ]

Di-[mu]-chlorido-bis(chlorido{2-[4-(dimethylamino)benzylideneamino]pyridine-[kappa]N}mercury(II))

Q. Wang and D. Wang

Abstract top

The title complex, [Hg2Cl4(C14H15N3)2], has a centre of symmetry at the centre of the four-membered ring formed by the two Hg and two bridging Cl atoms. Each HgII atom is four-coordinated in a distorted tetrahedral coordination geometry by one N atom from the pyridyl ring of a Schiff base ligand, two bridging Cl atoms and one terminal Cl atom. The Hg...Hg distance is 3.774 (2) Å. In the crystal structure, the molecules are linked into a two-dimensional network by intermolecular C-H...Cl hydrogen bonds.

Comment top

Schiff bases have been intensively investigated recently owing to their strong coordination capability and diverse biological activities, such as antibacterial, antitumor activities etc (Yang et al., 2000; Mondal et al., 2001; Tarafder et al., 2002). We report here the synthesis and crystal structure of the title compound, a new mercury(II) complex, with a monodentate Schiff base ligand derived from the condensation of p-dimethylaminobenzaldehyde and 2-aminopyridine.

The title complex (Fig.1) possesses a crystallographically imposed center of symmetry. The two crystallographically equivalent mercury atoms are bridged by two Cl atoms. Each HgII atom is four-coordinated in a distorted tetrahedral coordination geometry by one N atom from the pyridyl ring of a Schiff base ligand, two bridging Cl atoms and one terminal Cl atom. There is significant distortion from tetrahedral geometry, the angles about the metal ranging from 89.9 (3)–153.4 (3)° (Table 1).

As seen in Fig. 2, the molecules are linked into a two-dimensional framework by intermolecular C—H···Cl hydrogen bonds (Table 2).

Related literature top

For biological activity, see: Yang et al. (2000). For synthesis of related compounds, see: Mondal et al. (2001); Tarafder et al. (2002).

Experimental top

p-dimethylaminobenzaldehyde (1 mmol, 149.2 mg) in hot absolute ethanol (10 ml) was added dropwise to a absolute ethanol solution (5 ml) of 2-aminopyridine (1 mmol, 94.1 mg). The mixture was heated under reflux with stirring for 4 h. An absolute ethanol solution (5 ml) of mercury chloride (1 mmol, 217.2 mg) was then added dropwise, and the mixture was stirred at 323 K for another 8 h. The solution was kept at room temperature for about two weeks, after which large red-brown block-shaped crystals of the title complex suitable for X-ray diffraction analysis were obtained.

Refinement top

All H-atoms were positioned geometrically and refined using a riding model, with C—H = 0.96 (methylene) or 0.93 Å (aromatic) and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The structure of the title complex, showing 30% probability displacement ellipsoids and the atom-numbering scheme. Atoms labelled with the suffix A are generated by the symmetry operation (-x, 2 - y, 1 - z). H atoms have been omitted for clarity.
[Figure 2] Fig. 2. The crystal packing of the title complex, viewed approximately along the a axis.
Di-µ-Chlorido-bis({2-[4-(dimethylamino)benzylideneamino]pyridine-κN} chloridomercury(II)) top
Crystal data top
[Hg2Cl4(C14H15N3)2]Z = 1
Mr = 993.56F(000) = 468
Triclinic, P1Dx = 2.127 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 8.9474 (16) ÅCell parameters from 2345 reflections
b = 9.0853 (17) Åθ = 2.1–27.9°
c = 10.202 (2) ŵ = 10.26 mm−1
α = 73.597 (1)°T = 298 K
β = 79.807 (2)°Block, red-brown
γ = 79.619 (2)°0.28 × 0.27 × 0.27 mm
V = 775.5 (3) Å3
Data collection top
Siemens SMART CCD area-detector
diffractometer		2660 independent reflections
Radiation source: fine-focus sealed tube2239 reflections with I > 2σ(I)
graphiteRint = 0.037
φ and ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −10→7
Tmin = 0.161, Tmax = 0.168k = −10→10
3911 measured reflectionsl = −12→8
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.070Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.205H-atom parameters constrained
S = 1.05 w = 1/[σ2(Fo2) + (0.095P)2 + 4.2002P]
where P = (Fo2 + 2Fc2)/3
2660 reflections(Δ/σ)max = 0.001
183 parametersΔρmax = 3.62 e Å−3
0 restraintsΔρmin = −4.39 e Å−3
Crystal data top
[Hg2Cl4(C14H15N3)2]γ = 79.619 (2)°
Mr = 993.56V = 775.5 (3) Å3
Triclinic, P1Z = 1
a = 8.9474 (16) ÅMo Kα radiation
b = 9.0853 (17) ŵ = 10.26 mm−1
c = 10.202 (2) ÅT = 298 K
α = 73.597 (1)°0.28 × 0.27 × 0.27 mm
β = 79.807 (2)°
Data collection top
Siemens SMART CCD area-detector
diffractometer		2660 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2239 reflections with I > 2σ(I)
Tmin = 0.161, Tmax = 0.168Rint = 0.037
3911 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.070H-atom parameters constrained
wR(F2) = 0.205Δρmax = 3.62 e Å−3
S = 1.05Δρmin = −4.39 e Å−3
2660 reflectionsAbsolute structure: ?
183 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
Hg10.05073 (6)0.79012 (6)0.59293 (5)0.0476 (3)
Cl10.2155 (4)1.0226 (4)0.4919 (5)0.0523 (9)
Cl20.0013 (8)0.7687 (6)0.8306 (5)0.0838 (16)
N10.0817 (12)0.6988 (12)0.4132 (12)0.038 (2)
N20.2356 (12)0.5164 (12)0.5504 (12)0.040 (3)
N30.6090 (15)0.1517 (14)1.0596 (15)0.053 (3)
C10.1761 (14)0.5656 (14)0.4248 (13)0.033 (3)
C20.2015 (17)0.4915 (16)0.3185 (18)0.050 (4)
H20.26410.39670.32680.061*
C30.1337 (19)0.5597 (19)0.2026 (19)0.055 (4)
H30.15280.51300.12990.066*
C40.0369 (17)0.6973 (18)0.1926 (18)0.050 (4)
H4−0.01260.74210.11500.060*
C50.0144 (16)0.7676 (16)0.2981 (16)0.045 (3)
H5−0.04730.86280.29070.054*
C60.3453 (15)0.4021 (15)0.5702 (15)0.042 (3)
H60.38470.35530.49890.050*
C70.4084 (15)0.3450 (14)0.6964 (16)0.040 (3)
C80.5328 (15)0.2215 (15)0.7054 (16)0.044 (3)
H80.56960.18290.62880.053*
C90.5995 (15)0.1581 (15)0.8230 (18)0.047 (4)
H90.68020.07740.82530.057*
C100.5470 (16)0.2139 (15)0.9402 (16)0.043 (3)
C110.4236 (17)0.3374 (17)0.9313 (17)0.050 (4)
H110.38710.37741.00720.059*
C120.3575 (16)0.3986 (16)0.8127 (17)0.047 (3)
H120.27610.47850.81050.056*
C130.7362 (17)0.0248 (18)1.073 (2)0.061 (5)
H13A0.7170−0.05261.03330.091*
H13B0.7456−0.02031.16920.091*
H13C0.82960.06391.02650.091*
C140.546 (2)0.199 (2)1.184 (2)0.076 (5)
H14A0.53780.30961.16560.113*
H14B0.61200.15111.25380.113*
H14C0.44610.16771.21650.113*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Hg10.0615 (4)0.0461 (4)0.0394 (4)−0.0006 (3)−0.0138 (3)−0.0178 (3)
Cl10.0460 (18)0.0465 (18)0.067 (3)−0.0028 (14)−0.0047 (17)−0.0234 (18)
Cl20.139 (5)0.088 (3)0.038 (3)−0.039 (3)−0.005 (3)−0.026 (2)
N10.040 (5)0.037 (5)0.042 (7)−0.008 (4)−0.007 (5)−0.018 (5)
N20.046 (6)0.034 (5)0.037 (7)−0.003 (5)−0.005 (5)−0.007 (5)
N30.061 (7)0.041 (6)0.059 (9)−0.001 (6)−0.024 (7)−0.011 (6)
C10.044 (6)0.033 (6)0.025 (6)−0.013 (5)−0.007 (5)−0.003 (5)
C20.054 (8)0.039 (7)0.064 (11)−0.002 (6)−0.004 (8)−0.028 (7)
C30.064 (9)0.052 (8)0.065 (11)−0.017 (7)−0.008 (8)−0.035 (8)
C40.051 (8)0.053 (8)0.056 (10)−0.012 (7)−0.019 (7)−0.019 (7)
C50.050 (8)0.044 (7)0.043 (9)0.000 (6)−0.014 (7)−0.015 (6)
C60.043 (7)0.045 (7)0.034 (8)−0.003 (6)0.002 (6)−0.011 (6)
C70.041 (7)0.031 (6)0.048 (9)−0.003 (5)−0.008 (6)−0.007 (6)
C80.038 (6)0.039 (7)0.051 (9)0.003 (5)−0.005 (6)−0.012 (6)
C90.035 (6)0.030 (6)0.075 (11)−0.001 (5)−0.008 (7)−0.011 (7)
C100.050 (7)0.035 (6)0.050 (9)−0.014 (6)−0.018 (7)−0.008 (6)
C110.055 (8)0.044 (7)0.054 (10)0.001 (6)−0.011 (7)−0.022 (7)
C120.042 (7)0.037 (7)0.058 (10)0.010 (6)−0.018 (7)−0.011 (7)
C130.050 (8)0.049 (8)0.071 (12)0.004 (7)−0.028 (8)0.010 (8)
C140.095 (14)0.061 (10)0.067 (13)0.007 (10)−0.032 (11)−0.009 (9)
Geometric parameters (Å, °) top
Hg1—N12.173 (12)C5—H50.93
Hg1—Cl22.344 (5)C6—C71.42 (2)
Hg1—Cl12.655 (4)C6—H60.93
Hg1—Cl1i2.785 (4)C7—C121.38 (2)
Hg1—N22.825 (10)C7—C81.426 (17)
Cl1—Hg1i2.785 (4)C8—C91.37 (2)
N1—C11.334 (16)C8—H80.93
N1—C51.354 (19)C9—C101.40 (2)
N2—C61.291 (16)C9—H90.93
N2—C11.399 (17)C10—C111.421 (19)
N3—C101.36 (2)C11—C121.37 (2)
N3—C141.45 (2)C11—H110.93
N3—C131.462 (18)C12—H120.93
C1—C21.40 (2)C13—H13A0.96
C2—C31.36 (2)C13—H13B0.96
C2—H20.93C13—H13C0.96
C3—C41.38 (2)C14—H14A0.96
C3—H30.93C14—H14B0.96
C4—C51.37 (2)C14—H14C0.96
C4—H40.93
N1—Hg1—Cl2153.4 (3)C4—C5—H5119.9
N1—Hg1—Cl199.5 (3)N2—C6—C7122.8 (13)
Cl2—Hg1—Cl1104.57 (16)N2—C6—H6118.6
N1—Hg1—Cl1i89.9 (3)C7—C6—H6118.6
Cl2—Hg1—Cl1i100.32 (19)C12—C7—C6125.1 (12)
Cl1—Hg1—Cl1i92.18 (11)C12—C7—C8116.9 (14)
N1—Hg1—N252.0 (4)C6—C7—C8118.0 (13)
Cl2—Hg1—N2108.4 (3)C9—C8—C7122.1 (14)
Cl1—Hg1—N2108.2 (2)C9—C8—H8118.9
Cl1i—Hg1—N2138.5 (3)C7—C8—H8118.9
Hg1—Cl1—Hg1i87.82 (11)C8—C9—C10120.4 (12)
C1—N1—C5121.5 (12)C8—C9—H9119.8
C1—N1—Hg1113.7 (9)C10—C9—H9119.8
C5—N1—Hg1124.8 (9)N3—C10—C9121.9 (13)
C6—N2—C1120.2 (12)N3—C10—C11120.5 (14)
C6—N2—Hg1156.2 (11)C9—C10—C11117.6 (14)
C1—N2—Hg181.9 (7)C12—C11—C10121.1 (14)
C10—N3—C14122.0 (13)C12—C11—H11119.5
C10—N3—C13122.3 (15)C10—C11—H11119.5
C14—N3—C13115.5 (14)C11—C12—C7121.9 (12)
N1—C1—C2119.5 (13)C11—C12—H12119.1
N1—C1—N2112.3 (11)C7—C12—H12119.1
C2—C1—N2128.2 (12)N3—C13—H13A109.5
C3—C2—C1119.3 (13)N3—C13—H13B109.5
C3—C2—H2120.3H13A—C13—H13B109.5
C1—C2—H2120.3N3—C13—H13C109.5
C2—C3—C4120.2 (15)H13A—C13—H13C109.5
C2—C3—H3119.9H13B—C13—H13C109.5
C4—C3—H3119.9N3—C14—H14A109.5
C5—C4—C3119.2 (15)N3—C14—H14B109.5
C5—C4—H4120.4H14A—C14—H14B109.5
C3—C4—H4120.4N3—C14—H14C109.5
N1—C5—C4120.2 (13)H14A—C14—H14C109.5
N1—C5—H5119.9H14B—C14—H14C109.5
Symmetry codes: (i) −x, −y+2, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···Cl2ii0.932.823.626 (18)145
C5—H5···Cl1i0.932.803.433 (16)127
C8—H8···Cl1iii0.932.803.628 (15)148
Symmetry codes: (ii) x, y, z−1; (i) −x, −y+2, −z+1; (iii) −x+1, −y+1, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Hg1—N12.173 (12)Hg1—Cl12.655 (4)
Hg1—Cl22.344 (5)Hg1—Cl1i2.785 (4)
N1—Hg1—Cl2153.4 (3)N1—Hg1—Cl1i89.9 (3)
N1—Hg1—Cl199.5 (3)Cl2—Hg1—Cl1i100.32 (19)
Cl2—Hg1—Cl1104.57 (16)Cl1—Hg1—Cl1i92.18 (11)
Symmetry codes: (i) −x, −y+2, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C4—H4···Cl2ii0.932.823.626 (18)145
C5—H5···Cl1i0.932.803.433 (16)127
C8—H8···Cl1iii0.932.803.628 (15)148
Symmetry codes: (ii) x, y, z−1; (i) −x, −y+2, −z+1; (iii) −x+1, −y+1, −z+1.
Acknowledgements top

The authors acknowledge financial support from the Shandong Province Science Foundation, and the State Key Laboratory of Crystal Materials, Shandong University, People's Republic of China.

references
References top

Mondal, N., Mitra, S., Gramilich, V., Ghodsi, S. O. & Abdul Malik, K. M. (2001). Polyhedron, 20, 135–141.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXL97 and SHELXS97. University of Göttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Tarafder, M. T. H., Khoo, T.-J., Crouse, K. A., Ali, A. M., Yamin, B. M. & Fun, H.-K. (2002). Polyhedron, 21, 2691–2698.

Yang, Z.-Y., Yang, R.-D., Li, F.-S. & Yu, K.-B. (2000). Polyhedron, 19, 2599–2604.