Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807059983/lh2568sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807059983/lh2568Isup2.hkl |
CCDC reference: 672758
Tris(2-aminoethyl)amine (2 mmol, 292.5 mg) in hot absolute ethanol (10 ml) was added dropwise to a absolute ethanol solution (20 ml) of mercury chloride (4 mmol, 868.8 mg). The mixture was heated under reflux with stirring for 5 h. The solution was kept at room temperature for about 20 days, after which large yellow 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 0.97 (methylene) and N—H (amino) 0.90 Å, withUiso(H) =1.2Ueq(C,N).
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); 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 (Sheldrick, 1997b).
[Hg2Cl4(C6H18N4)] | F(000) = 1240 |
Mr = 689.22 | Dx = 2.930 Mg m−3 |
Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P2ybc | Cell parameters from 3679 reflections |
a = 10.4378 (6) Å | θ = 2.4–27.5° |
b = 11.5537 (8) Å | µ = 20.30 mm−1 |
c = 13.1306 (10) Å | T = 298 K |
β = 99.395 (1)° | Block, yellow |
V = 1562.25 (18) Å3 | 0.15 × 0.14 × 0.14 mm |
Z = 4 |
Siemens SMART CCD area-detector diffractometer | 2245 reflections with I > 2σ(I) |
Radiation source: fine-focus sealed tube | Rint = 0.058 |
ϕ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −10→12 |
Tmin = 0.151, Tmax = 0.163 | k = −13→13 |
7516 measured reflections | l = −15→11 |
2757 independent reflections |
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)] = 0.038 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.0433P)2 + 0.6626P] where P = (Fo2 + 2Fc2)/3 |
2757 reflections | (Δ/σ)max = 0.001 |
139 parameters | Δρmax = 1.69 e Å−3 |
1 restraint | Δρmin = −1.45 e Å−3 |
[Hg2Cl4(C6H18N4)] | V = 1562.25 (18) Å3 |
Mr = 689.22 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 10.4378 (6) Å | µ = 20.30 mm−1 |
b = 11.5537 (8) Å | T = 298 K |
c = 13.1306 (10) Å | 0.15 × 0.14 × 0.14 mm |
β = 99.395 (1)° |
Siemens SMART CCD area-detector diffractometer | 2757 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 2245 reflections with I > 2σ(I) |
Tmin = 0.151, Tmax = 0.163 | Rint = 0.058 |
7516 measured reflections |
R[F2 > 2σ(F2)] = 0.038 | 1 restraint |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.07 | Δρmax = 1.69 e Å−3 |
2757 reflections | Δρmin = −1.45 e Å−3 |
139 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 | 0.11574 (4) | 0.36983 (3) | 0.70931 (3) | 0.03894 (16) | |
Hg2 | −0.27774 (4) | 0.42828 (4) | 0.61195 (3) | 0.04422 (17) | |
Cl1 | −0.0774 (2) | 0.2723 (2) | 0.5996 (2) | 0.04422 (17) | |
Cl2 | −0.4650 (3) | 0.3269 (3) | 0.5348 (2) | 0.0615 (8) | |
Cl3 | −0.1733 (3) | 0.5903 (2) | 0.5366 (2) | 0.0507 (7) | |
Cl4 | −0.2391 (3) | 0.4612 (3) | 0.7999 (2) | 0.0567 (8) | |
N1 | 0.3069 (7) | 0.4444 (7) | 0.8345 (6) | 0.0341 (19) | |
N2 | 0.2892 (8) | 0.2545 (7) | 0.6860 (7) | 0.042 (2) | |
H2A | 0.2621 | 0.1810 | 0.6746 | 0.051* | |
H2B | 0.3217 | 0.2789 | 0.6304 | 0.051* | |
N3 | 0.0576 (8) | 0.3501 (8) | 0.8729 (7) | 0.044 (2) | |
H3A | −0.0271 | 0.3672 | 0.8698 | 0.052* | |
H3B | 0.0701 | 0.2765 | 0.8947 | 0.052* | |
N4 | 0.1280 (9) | 0.5653 (8) | 0.6750 (8) | 0.051 (2) | |
H4A | 0.1026 | 0.5784 | 0.6072 | 0.061* | |
H4B | 0.0752 | 0.6050 | 0.7101 | 0.061* | |
C1 | 0.4199 (10) | 0.3836 (10) | 0.8101 (9) | 0.045 (3) | |
H1A | 0.4875 | 0.3843 | 0.8703 | 0.054* | |
H1B | 0.4524 | 0.4243 | 0.7550 | 0.054* | |
C2 | 0.3906 (10) | 0.2588 (10) | 0.7772 (8) | 0.043 (3) | |
H2C | 0.4688 | 0.2223 | 0.7616 | 0.052* | |
H2D | 0.3623 | 0.2164 | 0.8333 | 0.052* | |
C3 | 0.2799 (9) | 0.4150 (9) | 0.9393 (7) | 0.038 (2) | |
H3C | 0.3298 | 0.4658 | 0.9897 | 0.045* | |
H3D | 0.3071 | 0.3361 | 0.9561 | 0.045* | |
C4 | 0.1357 (10) | 0.4275 (10) | 0.9452 (8) | 0.045 (3) | |
H4C | 0.1216 | 0.4101 | 1.0148 | 0.054* | |
H4D | 0.1089 | 0.5068 | 0.9298 | 0.054* | |
C5 | 0.3144 (11) | 0.5708 (9) | 0.8183 (9) | 0.047 (3) | |
H5A | 0.4038 | 0.5959 | 0.8373 | 0.057* | |
H5B | 0.2630 | 0.6102 | 0.8630 | 0.057* | |
C6 | 0.2654 (11) | 0.6044 (10) | 0.7069 (10) | 0.055 (3) | |
H6A | 0.2702 | 0.6877 | 0.6995 | 0.066* | |
H6B | 0.3200 | 0.5692 | 0.6624 | 0.066* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Hg1 | 0.0296 (3) | 0.0429 (3) | 0.0411 (3) | −0.00315 (17) | −0.00385 (17) | −0.00563 (17) |
Hg2 | 0.0362 (3) | 0.0502 (3) | 0.0459 (3) | −0.01336 (18) | 0.00534 (19) | −0.00858 (19) |
Cl1 | 0.0362 (3) | 0.0502 (3) | 0.0459 (3) | −0.01336 (18) | 0.00534 (19) | −0.00858 (19) |
Cl2 | 0.0410 (16) | 0.077 (2) | 0.061 (2) | −0.0240 (15) | −0.0089 (13) | −0.0014 (16) |
Cl3 | 0.0464 (16) | 0.0447 (15) | 0.0605 (19) | −0.0098 (13) | 0.0075 (13) | 0.0081 (13) |
Cl4 | 0.0558 (18) | 0.0717 (19) | 0.0395 (17) | 0.0081 (15) | −0.0019 (13) | −0.0160 (14) |
N1 | 0.027 (4) | 0.040 (5) | 0.036 (5) | 0.000 (4) | 0.005 (3) | −0.007 (4) |
N2 | 0.054 (5) | 0.039 (5) | 0.034 (5) | 0.006 (4) | 0.008 (4) | −0.010 (4) |
N3 | 0.031 (5) | 0.056 (6) | 0.045 (6) | −0.007 (4) | 0.009 (4) | 0.003 (4) |
N4 | 0.049 (6) | 0.044 (6) | 0.054 (6) | 0.012 (4) | −0.005 (4) | 0.006 (4) |
C1 | 0.022 (5) | 0.068 (8) | 0.045 (7) | 0.009 (5) | 0.007 (4) | −0.006 (6) |
C2 | 0.035 (6) | 0.056 (7) | 0.040 (6) | 0.012 (5) | 0.009 (5) | 0.001 (5) |
C3 | 0.034 (6) | 0.054 (6) | 0.023 (5) | 0.000 (5) | 0.000 (4) | −0.010 (5) |
C4 | 0.044 (6) | 0.059 (7) | 0.036 (6) | 0.007 (5) | 0.014 (5) | −0.006 (5) |
C5 | 0.054 (7) | 0.039 (6) | 0.049 (7) | −0.017 (5) | 0.009 (5) | −0.010 (5) |
C6 | 0.054 (8) | 0.045 (6) | 0.067 (9) | −0.001 (6) | 0.015 (6) | 0.008 (6) |
Hg1—N2 | 2.308 (8) | N4—C6 | 1.497 (14) |
Hg1—N4 | 2.310 (9) | N4—H4A | 0.9000 |
Hg1—N3 | 2.337 (8) | N4—H4B | 0.9000 |
Hg1—N1 | 2.521 (8) | C1—C2 | 1.521 (16) |
Hg1—Cl1 | 2.542 (2) | C1—H1A | 0.9700 |
Hg2—Cl2 | 2.361 (3) | C1—H1B | 0.9700 |
Hg2—Cl3 | 2.454 (3) | C2—H2C | 0.9700 |
Hg2—Cl4 | 2.465 (3) | C2—H2D | 0.9700 |
Hg2—Cl1 | 2.785 (3) | C3—C4 | 1.526 (13) |
N1—C1 | 1.452 (12) | C3—H3C | 0.9700 |
N1—C5 | 1.480 (13) | C3—H3D | 0.9700 |
N1—C3 | 1.488 (13) | C4—H4C | 0.9700 |
N2—C2 | 1.463 (13) | C4—H4D | 0.9700 |
N2—H2A | 0.9000 | C5—C6 | 1.519 (16) |
N2—H2B | 0.9000 | C5—H5A | 0.9700 |
N3—C4 | 1.453 (13) | C5—H5B | 0.9700 |
N3—H3A | 0.9000 | C6—H6A | 0.9700 |
N3—H3B | 0.9000 | C6—H6B | 0.9700 |
N2—Hg1—N4 | 118.0 (3) | Hg1—N4—H4B | 109.9 |
N2—Hg1—N3 | 113.1 (3) | H4A—N4—H4B | 108.3 |
N4—Hg1—N3 | 107.8 (3) | N1—C1—C2 | 112.8 (8) |
N2—Hg1—N1 | 74.3 (3) | N1—C1—H1A | 109.0 |
N4—Hg1—N1 | 74.3 (3) | C2—C1—H1A | 109.0 |
N3—Hg1—N1 | 74.4 (3) | N1—C1—H1B | 109.0 |
N2—Hg1—Cl1 | 103.6 (2) | C2—C1—H1B | 109.0 |
N4—Hg1—Cl1 | 112.8 (2) | H1A—C1—H1B | 107.8 |
N3—Hg1—Cl1 | 100.2 (2) | N2—C2—C1 | 110.5 (9) |
N1—Hg1—Cl1 | 172.4 (2) | N2—C2—H2C | 109.6 |
Cl2—Hg2—Cl3 | 126.63 (10) | C1—C2—H2C | 109.6 |
Cl2—Hg2—Cl4 | 119.67 (11) | N2—C2—H2D | 109.6 |
Cl3—Hg2—Cl4 | 105.97 (11) | C1—C2—H2D | 109.6 |
Cl2—Hg2—Cl1 | 103.36 (10) | H2C—C2—H2D | 108.1 |
Cl3—Hg2—Cl1 | 94.75 (9) | N1—C3—C4 | 111.3 (8) |
Cl4—Hg2—Cl1 | 99.00 (9) | N1—C3—H3C | 109.4 |
Hg1—Cl1—Hg2 | 102.34 (9) | C4—C3—H3C | 109.4 |
C1—N1—C5 | 112.5 (8) | N1—C3—H3D | 109.4 |
C1—N1—C3 | 112.1 (8) | C4—C3—H3D | 109.4 |
C5—N1—C3 | 112.3 (8) | H3C—C3—H3D | 108.0 |
C1—N1—Hg1 | 106.0 (6) | N3—C4—C3 | 111.2 (8) |
C5—N1—Hg1 | 107.4 (6) | N3—C4—H4C | 109.4 |
C3—N1—Hg1 | 106.0 (5) | C3—C4—H4C | 109.4 |
C2—N2—Hg1 | 110.5 (6) | N3—C4—H4D | 109.4 |
C2—N2—H2A | 109.6 | C3—C4—H4D | 109.4 |
Hg1—N2—H2A | 109.6 | H4C—C4—H4D | 108.0 |
C2—N2—H2B | 109.6 | N1—C5—C6 | 111.9 (9) |
Hg1—N2—H2B | 109.6 | N1—C5—H5A | 109.2 |
H2A—N2—H2B | 108.1 | C6—C5—H5A | 109.2 |
C4—N3—Hg1 | 109.8 (6) | N1—C5—H5B | 109.2 |
C4—N3—H3A | 109.7 | C6—C5—H5B | 109.2 |
Hg1—N3—H3A | 109.7 | H5A—C5—H5B | 107.9 |
C4—N3—H3B | 109.7 | N4—C6—C5 | 110.4 (9) |
Hg1—N3—H3B | 109.7 | N4—C6—H6A | 109.6 |
H3A—N3—H3B | 108.2 | C5—C6—H6A | 109.6 |
C6—N4—Hg1 | 108.8 (6) | N4—C6—H6B | 109.6 |
C6—N4—H4A | 109.9 | C5—C6—H6B | 109.6 |
Hg1—N4—H4A | 109.9 | H6A—C6—H6B | 108.1 |
C6—N4—H4B | 109.9 |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···Cl3i | 0.90 | 2.51 | 3.378 (9) | 163 |
N2—H2B···Cl2ii | 0.90 | 2.78 | 3.590 (9) | 150 |
N2—H2A···Cl4i | 0.90 | 2.58 | 3.438 (9) | 160 |
C5—H5B···Cl1iii | 0.97 | 2.80 | 3.684 (12) | 153 |
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) x+1, y, z; (iii) −x, y+1/2, −z+3/2. |
Experimental details
Crystal data | |
Chemical formula | [Hg2Cl4(C6H18N4)] |
Mr | 689.22 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 298 |
a, b, c (Å) | 10.4378 (6), 11.5537 (8), 13.1306 (10) |
β (°) | 99.395 (1) |
V (Å3) | 1562.25 (18) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 20.30 |
Crystal size (mm) | 0.15 × 0.14 × 0.14 |
Data collection | |
Diffractometer | Siemens SMART CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 1996) |
Tmin, Tmax | 0.151, 0.163 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7516, 2757, 2245 |
Rint | 0.058 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.038, 0.103, 1.07 |
No. of reflections | 2757 |
No. of parameters | 139 |
No. of restraints | 1 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 1.69, −1.45 |
Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 1997a), SHELXL97 (Sheldrick, 1997a), SHELXTL (Sheldrick, 1997b).
Hg1—N2 | 2.308 (8) | Hg2—Cl2 | 2.361 (3) |
Hg1—N4 | 2.310 (9) | Hg2—Cl3 | 2.454 (3) |
Hg1—N3 | 2.337 (8) | Hg2—Cl4 | 2.465 (3) |
Hg1—N1 | 2.521 (8) | Hg2—Cl1 | 2.785 (3) |
Hg1—Cl1 | 2.542 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N3—H3B···Cl3i | 0.90 | 2.51 | 3.378 (9) | 163.1 |
N2—H2B···Cl2ii | 0.90 | 2.78 | 3.590 (9) | 149.8 |
N2—H2A···Cl4i | 0.90 | 2.58 | 3.438 (9) | 160.3 |
C5—H5B···Cl1iii | 0.97 | 2.80 | 3.684 (12) | 152.7 |
Symmetry codes: (i) −x, y−1/2, −z+3/2; (ii) x+1, y, z; (iii) −x, y+1/2, −z+3/2. |
Research of organic polyamines is currently of great insterest because of their potential applications as useful organic ligands, in which the amine nitrogen atoms have strong coordination ablity to transition metal ions and recongnition function (Adam et al., 1988; Marchetti et al., 1989; Dakternicks, 1990; Adam et al., 1994). Their transition metal complexes play an excellent role in catalysis and mimic studies on dismutase and chlorophyll (Gou et al., 1993; Cai et al., 1997; Wang et al., 1997). In this paper, we report the synthesis and crystal structure of the title compound.
The molecular structure of the title bimetallic and bridged complex (C6H18N4)Hg—Cl—HgCl3 (I) is shown in Fig. 1. The coordination geometry around Hg1 atom can be described as distorted trigonal bipyramidal with the axial positions occupied by the N1 and Cl1 atoms (N1— Hg1— Cl1 = 172.4 (2) °). Atom Hg2 is four-coordinated in a distorted tetrahedral coordination geometry by one bridging Cl atoms and three terminal Cl atoms. The bond distances of Hg—N are in the range of 2.308 (8) – 2.521 (8) Å, the bond distances of Hg—Cl are in the range of 2.361 (3) – 2.785 (3) Å. Tris(2-aminoethyl)amine ligand consists of three five-membered chelate rings, the dihedral angle between the mean planes of these chelate rings range from 55.80 (0.28) to to 64.12 (0.31) °.
In the crystal structure, adjacent molecules are linked by intermolecular N—H···Cl hydrogen bonds into a two-dimensional network which is further stabilzed by weak intermolecular C—H···Cl hydrogen bonds (Fig. 2).