Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807032047/ci2406sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807032047/ci2406Isup2.hkl |
CCDC reference: 622099
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.
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).
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).
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.
[Hg2Cl4(C14H15N3)2] | Z = 1 |
Mr = 993.56 | F(000) = 468 |
Triclinic, P1 | Dx = 2.127 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.9474 (16) Å | Cell parameters from 2345 reflections |
b = 9.0853 (17) Å | θ = 2.1–27.9° |
c = 10.202 (2) Å | µ = 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 |
Siemens SMART CCD area-detector diffractometer | 2660 independent reflections |
Radiation source: fine-focus sealed tube | 2239 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
φ and ω scans | θmax = 25.0°, θmin = 2.1° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→7 |
Tmin = 0.161, Tmax = 0.168 | k = −10→10 |
3911 measured reflections | l = −12→8 |
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.070 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.205 | H-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 parameters | Δρmax = 3.62 e Å−3 |
0 restraints | Δρmin = −4.39 e Å−3 |
[Hg2Cl4(C14H15N3)2] | γ = 79.619 (2)° |
Mr = 993.56 | V = 775.5 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 8.9474 (16) Å | Mo Kα radiation |
b = 9.0853 (17) Å | µ = 10.26 mm−1 |
c = 10.202 (2) Å | T = 298 K |
α = 73.597 (1)° | 0.28 × 0.27 × 0.27 mm |
β = 79.807 (2)° |
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 = 0.168 | Rint = 0.037 |
3911 measured reflections |
R[F2 > 2σ(F2)] = 0.070 | 0 restraints |
wR(F2) = 0.205 | H-atom parameters constrained |
S = 1.05 | Δρmax = 3.62 e Å−3 |
2660 reflections | Δρmin = −4.39 e Å−3 |
183 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. |
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. |
x | y | z | Uiso*/Ueq | ||
Hg1 | 0.05073 (6) | 0.79012 (6) | 0.59293 (5) | 0.0476 (3) | |
Cl1 | 0.2155 (4) | 1.0226 (4) | 0.4919 (5) | 0.0523 (9) | |
Cl2 | 0.0013 (8) | 0.7687 (6) | 0.8306 (5) | 0.0838 (16) | |
N1 | 0.0817 (12) | 0.6988 (12) | 0.4132 (12) | 0.038 (2) | |
N2 | 0.2356 (12) | 0.5164 (12) | 0.5504 (12) | 0.040 (3) | |
N3 | 0.6090 (15) | 0.1517 (14) | 1.0596 (15) | 0.053 (3) | |
C1 | 0.1761 (14) | 0.5656 (14) | 0.4248 (13) | 0.033 (3) | |
C2 | 0.2015 (17) | 0.4915 (16) | 0.3185 (18) | 0.050 (4) | |
H2 | 0.2641 | 0.3967 | 0.3268 | 0.061* | |
C3 | 0.1337 (19) | 0.5597 (19) | 0.2026 (19) | 0.055 (4) | |
H3 | 0.1528 | 0.5130 | 0.1299 | 0.066* | |
C4 | 0.0369 (17) | 0.6973 (18) | 0.1926 (18) | 0.050 (4) | |
H4 | −0.0126 | 0.7421 | 0.1150 | 0.060* | |
C5 | 0.0144 (16) | 0.7676 (16) | 0.2981 (16) | 0.045 (3) | |
H5 | −0.0473 | 0.8628 | 0.2907 | 0.054* | |
C6 | 0.3453 (15) | 0.4021 (15) | 0.5702 (15) | 0.042 (3) | |
H6 | 0.3847 | 0.3553 | 0.4989 | 0.050* | |
C7 | 0.4084 (15) | 0.3450 (14) | 0.6964 (16) | 0.040 (3) | |
C8 | 0.5328 (15) | 0.2215 (15) | 0.7054 (16) | 0.044 (3) | |
H8 | 0.5696 | 0.1829 | 0.6288 | 0.053* | |
C9 | 0.5995 (15) | 0.1581 (15) | 0.8230 (18) | 0.047 (4) | |
H9 | 0.6802 | 0.0774 | 0.8253 | 0.057* | |
C10 | 0.5470 (16) | 0.2139 (15) | 0.9402 (16) | 0.043 (3) | |
C11 | 0.4236 (17) | 0.3374 (17) | 0.9313 (17) | 0.050 (4) | |
H11 | 0.3871 | 0.3774 | 1.0072 | 0.059* | |
C12 | 0.3575 (16) | 0.3986 (16) | 0.8127 (17) | 0.047 (3) | |
H12 | 0.2761 | 0.4785 | 0.8105 | 0.056* | |
C13 | 0.7362 (17) | 0.0248 (18) | 1.073 (2) | 0.061 (5) | |
H13A | 0.7170 | −0.0526 | 1.0333 | 0.091* | |
H13B | 0.7456 | −0.0203 | 1.1692 | 0.091* | |
H13C | 0.8296 | 0.0639 | 1.0265 | 0.091* | |
C14 | 0.546 (2) | 0.199 (2) | 1.184 (2) | 0.076 (5) | |
H14A | 0.5378 | 0.3096 | 1.1656 | 0.113* | |
H14B | 0.6120 | 0.1511 | 1.2538 | 0.113* | |
H14C | 0.4461 | 0.1677 | 1.2165 | 0.113* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.0615 (4) | 0.0461 (4) | 0.0394 (4) | −0.0006 (3) | −0.0138 (3) | −0.0178 (3) |
Cl1 | 0.0460 (18) | 0.0465 (18) | 0.067 (3) | −0.0028 (14) | −0.0047 (17) | −0.0234 (18) |
Cl2 | 0.139 (5) | 0.088 (3) | 0.038 (3) | −0.039 (3) | −0.005 (3) | −0.026 (2) |
N1 | 0.040 (5) | 0.037 (5) | 0.042 (7) | −0.008 (4) | −0.007 (5) | −0.018 (5) |
N2 | 0.046 (6) | 0.034 (5) | 0.037 (7) | −0.003 (5) | −0.005 (5) | −0.007 (5) |
N3 | 0.061 (7) | 0.041 (6) | 0.059 (9) | −0.001 (6) | −0.024 (7) | −0.011 (6) |
C1 | 0.044 (6) | 0.033 (6) | 0.025 (6) | −0.013 (5) | −0.007 (5) | −0.003 (5) |
C2 | 0.054 (8) | 0.039 (7) | 0.064 (11) | −0.002 (6) | −0.004 (8) | −0.028 (7) |
C3 | 0.064 (9) | 0.052 (8) | 0.065 (11) | −0.017 (7) | −0.008 (8) | −0.035 (8) |
C4 | 0.051 (8) | 0.053 (8) | 0.056 (10) | −0.012 (7) | −0.019 (7) | −0.019 (7) |
C5 | 0.050 (8) | 0.044 (7) | 0.043 (9) | 0.000 (6) | −0.014 (7) | −0.015 (6) |
C6 | 0.043 (7) | 0.045 (7) | 0.034 (8) | −0.003 (6) | 0.002 (6) | −0.011 (6) |
C7 | 0.041 (7) | 0.031 (6) | 0.048 (9) | −0.003 (5) | −0.008 (6) | −0.007 (6) |
C8 | 0.038 (6) | 0.039 (7) | 0.051 (9) | 0.003 (5) | −0.005 (6) | −0.012 (6) |
C9 | 0.035 (6) | 0.030 (6) | 0.075 (11) | −0.001 (5) | −0.008 (7) | −0.011 (7) |
C10 | 0.050 (7) | 0.035 (6) | 0.050 (9) | −0.014 (6) | −0.018 (7) | −0.008 (6) |
C11 | 0.055 (8) | 0.044 (7) | 0.054 (10) | 0.001 (6) | −0.011 (7) | −0.022 (7) |
C12 | 0.042 (7) | 0.037 (7) | 0.058 (10) | 0.010 (6) | −0.018 (7) | −0.011 (7) |
C13 | 0.050 (8) | 0.049 (8) | 0.071 (12) | 0.004 (7) | −0.028 (8) | 0.010 (8) |
C14 | 0.095 (14) | 0.061 (10) | 0.067 (13) | 0.007 (10) | −0.032 (11) | −0.009 (9) |
Hg1—N1 | 2.173 (12) | C5—H5 | 0.93 |
Hg1—Cl2 | 2.344 (5) | C6—C7 | 1.42 (2) |
Hg1—Cl1 | 2.655 (4) | C6—H6 | 0.93 |
Hg1—Cl1i | 2.785 (4) | C7—C12 | 1.38 (2) |
Hg1—N2 | 2.825 (10) | C7—C8 | 1.426 (17) |
Cl1—Hg1i | 2.785 (4) | C8—C9 | 1.37 (2) |
N1—C1 | 1.334 (16) | C8—H8 | 0.93 |
N1—C5 | 1.354 (19) | C9—C10 | 1.40 (2) |
N2—C6 | 1.291 (16) | C9—H9 | 0.93 |
N2—C1 | 1.399 (17) | C10—C11 | 1.421 (19) |
N3—C10 | 1.36 (2) | C11—C12 | 1.37 (2) |
N3—C14 | 1.45 (2) | C11—H11 | 0.93 |
N3—C13 | 1.462 (18) | C12—H12 | 0.93 |
C1—C2 | 1.40 (2) | C13—H13A | 0.96 |
C2—C3 | 1.36 (2) | C13—H13B | 0.96 |
C2—H2 | 0.93 | C13—H13C | 0.96 |
C3—C4 | 1.38 (2) | C14—H14A | 0.96 |
C3—H3 | 0.93 | C14—H14B | 0.96 |
C4—C5 | 1.37 (2) | C14—H14C | 0.96 |
C4—H4 | 0.93 | ||
N1—Hg1—Cl2 | 153.4 (3) | C4—C5—H5 | 119.9 |
N1—Hg1—Cl1 | 99.5 (3) | N2—C6—C7 | 122.8 (13) |
Cl2—Hg1—Cl1 | 104.57 (16) | N2—C6—H6 | 118.6 |
N1—Hg1—Cl1i | 89.9 (3) | C7—C6—H6 | 118.6 |
Cl2—Hg1—Cl1i | 100.32 (19) | C12—C7—C6 | 125.1 (12) |
Cl1—Hg1—Cl1i | 92.18 (11) | C12—C7—C8 | 116.9 (14) |
N1—Hg1—N2 | 52.0 (4) | C6—C7—C8 | 118.0 (13) |
Cl2—Hg1—N2 | 108.4 (3) | C9—C8—C7 | 122.1 (14) |
Cl1—Hg1—N2 | 108.2 (2) | C9—C8—H8 | 118.9 |
Cl1i—Hg1—N2 | 138.5 (3) | C7—C8—H8 | 118.9 |
Hg1—Cl1—Hg1i | 87.82 (11) | C8—C9—C10 | 120.4 (12) |
C1—N1—C5 | 121.5 (12) | C8—C9—H9 | 119.8 |
C1—N1—Hg1 | 113.7 (9) | C10—C9—H9 | 119.8 |
C5—N1—Hg1 | 124.8 (9) | N3—C10—C9 | 121.9 (13) |
C6—N2—C1 | 120.2 (12) | N3—C10—C11 | 120.5 (14) |
C6—N2—Hg1 | 156.2 (11) | C9—C10—C11 | 117.6 (14) |
C1—N2—Hg1 | 81.9 (7) | C12—C11—C10 | 121.1 (14) |
C10—N3—C14 | 122.0 (13) | C12—C11—H11 | 119.5 |
C10—N3—C13 | 122.3 (15) | C10—C11—H11 | 119.5 |
C14—N3—C13 | 115.5 (14) | C11—C12—C7 | 121.9 (12) |
N1—C1—C2 | 119.5 (13) | C11—C12—H12 | 119.1 |
N1—C1—N2 | 112.3 (11) | C7—C12—H12 | 119.1 |
C2—C1—N2 | 128.2 (12) | N3—C13—H13A | 109.5 |
C3—C2—C1 | 119.3 (13) | N3—C13—H13B | 109.5 |
C3—C2—H2 | 120.3 | H13A—C13—H13B | 109.5 |
C1—C2—H2 | 120.3 | N3—C13—H13C | 109.5 |
C2—C3—C4 | 120.2 (15) | H13A—C13—H13C | 109.5 |
C2—C3—H3 | 119.9 | H13B—C13—H13C | 109.5 |
C4—C3—H3 | 119.9 | N3—C14—H14A | 109.5 |
C5—C4—C3 | 119.2 (15) | N3—C14—H14B | 109.5 |
C5—C4—H4 | 120.4 | H14A—C14—H14B | 109.5 |
C3—C4—H4 | 120.4 | N3—C14—H14C | 109.5 |
N1—C5—C4 | 120.2 (13) | H14A—C14—H14C | 109.5 |
N1—C5—H5 | 119.9 | H14B—C14—H14C | 109.5 |
Symmetry code: (i) −x, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···Cl2ii | 0.93 | 2.82 | 3.626 (18) | 145 |
C5—H5···Cl1i | 0.93 | 2.80 | 3.433 (16) | 127 |
C8—H8···Cl1iii | 0.93 | 2.80 | 3.628 (15) | 148 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y, z−1; (iii) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Hg2Cl4(C14H15N3)2] |
Mr | 993.56 |
Crystal system, space group | Triclinic, 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) |
V (Å3) | 775.5 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 10.26 |
Crystal size (mm) | 0.28 × 0.27 × 0.27 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.161, 0.168 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 3911, 2660, 2239 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.070, 0.205, 1.05 |
No. of reflections | 2660 |
No. of parameters | 183 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 3.62, −4.39 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SAINT, SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b), SHELXTL.
Hg1—N1 | 2.173 (12) | Hg1—Cl1 | 2.655 (4) |
Hg1—Cl2 | 2.344 (5) | Hg1—Cl1i | 2.785 (4) |
N1—Hg1—Cl2 | 153.4 (3) | N1—Hg1—Cl1i | 89.9 (3) |
N1—Hg1—Cl1 | 99.5 (3) | Cl2—Hg1—Cl1i | 100.32 (19) |
Cl2—Hg1—Cl1 | 104.57 (16) | Cl1—Hg1—Cl1i | 92.18 (11) |
Symmetry code: (i) −x, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C4—H4···Cl2ii | 0.93 | 2.82 | 3.626 (18) | 145 |
C5—H5···Cl1i | 0.93 | 2.80 | 3.433 (16) | 127 |
C8—H8···Cl1iii | 0.93 | 2.80 | 3.628 (15) | 148 |
Symmetry codes: (i) −x, −y+2, −z+1; (ii) x, y, z−1; (iii) −x+1, −y+1, −z+1. |
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).