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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032047/ci2406sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032047/ci2406Isup2.hkl
Contains datablock I

CCDC reference: 622099

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.020 Å
  • R factor = 0.069
  • wR factor = 0.205
  • Data-to-parameter ratio = 14.5

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low ....... 0.97 PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ............. 0.76 PLAT062_ALERT_4_C Rescale T(min) & T(max) by ..................... 0.37 PLAT342_ALERT_3_C Low Bond Precision on C-C Bonds (x 1000) Ang ... 20
Alert level G ABSTM02_ALERT_3_G When printed, the submitted absorption T values will be replaced by the scaled T values. Since the ratio of scaled T's is identical to the ratio of reported T values, the scaling does not imply a change to the absorption corrections used in the study. Ratio of Tmax expected/reported 0.372 Tmax scaled 0.063 Tmin scaled 0.060
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 1 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 0 ALERT type 2 Indicator that the structure model may be wrong or deficient 4 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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).

Structure description 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).

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

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 m3
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 mm1
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)
Graphite monochromatorRint = 0.037
φ and ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 107
Tmin = 0.161, Tmax = 0.168k = 1010
3911 measured reflectionsl = 128
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 Å3
0 restraintsΔρmin = 4.39 e Å3
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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0700 restraints
wR(F2) = 0.205H-atom parameters constrained
S = 1.05Δρmax = 3.62 e Å3
2660 reflectionsΔρmin = 4.39 e Å3
183 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.

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)
H40.01260.74210.11500.060*
C50.0144 (16)0.7676 (16)0.2981 (16)0.045 (3)
H50.04730.86280.29070.054*
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)
H13A0.71700.05261.03330.091*
H13B0.74560.02031.16920.091*
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, º) 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 code: (i) x, y+2, z+1.
Hydrogen-bond geometry (Å, º) 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: (i) x, y+2, z+1; (ii) x, y, z1; (iii) x+1, y+1, z+1.

Experimental details

Crystal data
Chemical formula[Hg2Cl4(C14H15N3)2]
Mr993.56
Crystal system, space groupTriclinic, P1
Temperature (K)298
a, b, c (Å)8.9474 (16), 9.0853 (17), 10.202 (2)
α, β, γ (°)73.597 (1), 79.807 (2), 79.619 (2)
V3)775.5 (3)
Z1
Radiation typeMo Kα
µ (mm1)10.26
Crystal size (mm)0.28 × 0.27 × 0.27
Data collection
DiffractometerSiemens SMART CCD area-detector
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.161, 0.168
No. of measured, independent and
observed [I > 2σ(I)] reflections
3911, 2660, 2239
Rint0.037
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.070, 0.205, 1.05
No. of reflections2660
No. of parameters183
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)3.62, 4.39

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.

Selected geometric parameters (Å, º) 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 code: (i) x, y+2, z+1.
Hydrogen-bond geometry (Å, º) 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: (i) x, y+2, z+1; (ii) x, y, z1; (iii) x+1, y+1, z+1.
 

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