PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2009 December 1; 65(Pt 12): m1645.
Published online 2009 November 21. doi:  10.1107/S1600536809049289
PMCID: PMC2971919

Dichloridobis(1,10-phenanthroline-5,6-dione-κ2 N,N′)mercury(II)

Abstract

In the title compound, [HgCl2(C12H6N2O2)2], the HgII atom is located on a twofold rotation axis and exists within a distorted octa­hedral geometry defined by a cis-Cl2N4 donor set. Mol­ecules are connected into layers in the ac plane via extensive C—H(...)Cl contacts as each Cl atom forms two such inter­actions. Contacts between the layers are of the type C=O(...)π [O(...)centroid distance = 3.110 (8) Å].

Related literature

For related main-group compounds of 1,10-phenanthroline-5,6-dione, see: de Alencastro et al. (2005 [triangle]). For the ligand synthesis, see: Yamada et al. (1992 [triangle]). For a related structure, see: Ramezanipour et al. (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1645-scheme1.jpg

Experimental

Crystal data

  • [HgCl2(C12H6N2O2)2]
  • M r = 691.87
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1645-efi1.jpg
  • a = 8.2261 (2) Å
  • b = 42.6761 (11) Å
  • c = 12.6108 (3) Å
  • V = 4427.12 (19) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 7.24 mm−1
  • T = 120 K
  • 0.20 × 0.10 × 0.06 mm

Data collection

  • Nonius KappaCCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.204, T max = 0.651
  • 10751 measured reflections
  • 2487 independent reflections
  • 2239 reflections with I > 2σ(I)
  • R int = 0.075

Refinement

  • R[F 2 > 2σ(F 2)] = 0.037
  • wR(F 2) = 0.094
  • S = 1.05
  • 2487 reflections
  • 159 parameters
  • 1 restraint
  • H-atom parameters constrained
  • Δρmax = 2.27 e Å−3
  • Δρmin = −0.68 e Å−3
  • Absolute structure: Flack (1983 [triangle]), 1163 Friedel pairs
  • Flack parameter: −0.012 (13)

Data collection: COLLECT (Hooft, 1998 [triangle]); cell refinement: DENZO (Otwinowski & Minor, 1997 [triangle]) and COLLECT; data reduction: DENZO and COLLECT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: DIAMOND (Brandenburg, 1999 [triangle]); software used to prepare material for publication: publCIF (Westrip, 2009 [triangle]).

Table 1
Selected bond lengths (Å)
Table 2
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809049289/hy2254sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809049289/hy2254Isup2.hkl

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

Acknowledgments

The use of the EPSRC X-ray crystallographic service at the University of Southampton, England, and the valuable assistance of the staff there are gratefully acknowledged. JLW acknowledges support from FAPEMIG (Brazil).

supplementary crystallographic information

Comment

In continuation of the previous studies of coordination compounds of 1,10-phenanthroline-5,6-dione (pdon) ligand (de Alencastro et al., 2005), the title compound, HgCl2(pdon)2, was investigated. The reaction of HgCl2 with pdon (1:1 mol ratio) led to the isolation of a pure 1:1 complex, HgCl2(pdon). However, as the product was unsuitable for X-ray crystallography, a further recrystallization from MeNO2 solution was attempted, which led to the isolation of the title compound, a 1:2 complex. Of interest was that the 1:1 HgI2(pdon) complex, prepared similarly to the chloride analogue, was recovered on recrystallization from MeNO2. Unfortunately this set of crystals also proved unsuitable for X-ray crystallography.

In the title compound, the HgII atom lies on a crystallographic twofold axis and exists within a cis-Cl2N4 donor set defined by two Cl atoms and four N atoms derived from two chelating pdon ligands (Fig. 1). There is a small disparity in the magnitude of the Hg—N bond distances, with Hg—N1 of 2.439 (7) Å being shorter than Hg—N2 of 2.512 (6) Å. Distortions from an ideal octahedral geometry are related in part to the acute chelate angle of 66.9 (2)°. The pdon ligand is essentially planar with a RMS of 0.226 Å for the N and C atoms, with O1 and O2 atoms lying, respectively, -0.079 (12) and 0.071 (13) Å out of the least-squares plane. The dihedral angle formed between the symmetry related 1,10-phenanthroline planes is 87.13 (11)°. The structural features described herein for the title compound resemble those found for HgCl2(1,10-phenanthroline)2 (Ramezanipour et al., 2005).

In the crystal structure, C—H···Cl interactions are found so that each Cl atom is associated with two H atoms to form supramolecular arrays in the ac plane (Table 1 and Fig. 2). The most prominent interactions between the layers are of the type C═O···π. The closest of these involves the carbonyl-O1 group and the centroid (Cg) of C4–C7, C11, C12 ring [O1···Cgi = 3.110 (8) Å with the C5–O1···Cgi angle being 133.1 (8)°, symmetry code: (i) -1/4+x, 1/4-y, -1/4+z] (Fig. 3).

Experimental

Solutions of HgCl2 (0.272 mg, 1.0 mmol) in EtOH (5 ml) and of 1,10-phenanthroline-5,6-dione (Yamada et al., 1992) (0.212 mg, 1.0 mmol) in EtOH (20 ml) were mixed and stirred at room temperature for 1 h. The precipitate was collected, washed with small portions of EtOH and petroleum ether and dried (yield 0.330 mg). Analysis, calculated for C12H6Cl2HgN2O2 [HgCl2(pdon)]: C 29.9, H 1.3, N 5.8%; found: C 30.2, H 1.5, N 5.2%.

Recrystallization of HgCl2(pdon) from MeNO2 solution produced crystals of the title compound, HgCl2(pdon)2.

Refinement

H atoms were geometrically placed with C—H = 0.95 Å, and refined as riding with Uiso(H) = 1.2Ueq(C). The maximum and minimum residual electron density peaks of 2.27 and 0.68 e Å-3 were located 0.91 and 0.82 Å from Hg atom, respectively.

Figures

Fig. 1.
Molecular structure of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry code: (i) -x, -y, z.]
Fig. 2.
Supramolecular array in the ac plane mediated by C—H···Cl contacts (orange dashed lines). [Colour codes: Hg orange; Cl cyan; O red; N blue; C grey; H green.]
Fig. 3.
Unit-cell contents viewed in projection down the a axis. The C—H···Cl contacts are shown as orange dashed lines. [Colour codes: Hg orange; Cl cyan; O red; N blue; C grey; H green.]

Crystal data

[HgCl2(C12H6N2O2)2]F(000) = 2640
Mr = 691.87Dx = 2.076 Mg m3
Orthorhombic, Fdd2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2dCell parameters from 18660 reflections
a = 8.2261 (2) Åθ = 2.9–27.5°
b = 42.6761 (11) ŵ = 7.24 mm1
c = 12.6108 (3) ÅT = 120 K
V = 4427.12 (19) Å3Block, yellow
Z = 80.20 × 0.10 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer2487 independent reflections
Radiation source: Enraf Nonius FR591 rotating anode2239 reflections with I > 2σ(I)
10 cm confocal mirrorsRint = 0.075
Detector resolution: 9.091 pixels mm-1θmax = 27.5°, θmin = 3.0°
[var phi] and ω scansh = −10→8
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)k = −55→55
Tmin = 0.204, Tmax = 0.651l = −16→16
10751 measured reflections

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.037H-atom parameters constrained
wR(F2) = 0.094w = 1/[σ2(Fo2) + (0.0564P)2 + 3.1352P] where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
2487 reflectionsΔρmax = 2.27 e Å3
159 parametersΔρmin = −0.68 e Å3
1 restraintAbsolute structure: Flack (1983), 1163 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.012 (13)

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)

xyzUiso*/Ueq
Hg0.00000.00000.48512 (8)0.04052 (12)
Cl10.1811 (2)0.03035 (5)0.61020 (15)0.0486 (4)
O1−0.3649 (8)0.12440 (15)0.2228 (6)0.072 (2)
O2−0.0592 (10)0.12581 (18)0.1361 (7)0.081 (2)
N1−0.2157 (8)0.03565 (16)0.4299 (5)0.0406 (14)
N20.0815 (7)0.03486 (14)0.3337 (4)0.0399 (13)
C1−0.3618 (9)0.03505 (19)0.4754 (6)0.0472 (16)
H1−0.38400.01910.52580.057*
C2−0.4837 (9)0.0567 (2)0.4528 (7)0.050 (2)
H2−0.58690.05540.48640.060*
C3−0.4507 (11)0.07993 (18)0.3806 (6)0.0459 (17)
H3−0.53000.09550.36530.055*
C4−0.3014 (10)0.08061 (18)0.3300 (6)0.0435 (16)
C5−0.2664 (10)0.1051 (2)0.2493 (14)0.057 (3)
C6−0.0923 (11)0.1052 (2)0.1979 (8)0.059 (2)
C70.0217 (9)0.0800 (2)0.2297 (7)0.0450 (17)
C80.1742 (11)0.0790 (2)0.1830 (6)0.0482 (18)
H80.20710.09450.13350.058*
C90.2777 (9)0.0545 (2)0.2110 (6)0.0453 (18)
H90.38180.05260.17920.054*
C100.2257 (10)0.03325 (19)0.2861 (7)0.0437 (17)
H100.29650.01660.30470.052*
C11−0.0196 (9)0.05763 (18)0.3047 (6)0.0409 (16)
C12−0.1850 (9)0.05809 (16)0.3578 (7)0.0413 (14)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Hg0.03662 (19)0.04817 (18)0.03677 (16)0.00021 (19)0.0000.000
Cl10.0400 (9)0.0635 (11)0.0424 (9)−0.0042 (8)−0.0003 (8)−0.0077 (8)
O10.062 (4)0.064 (4)0.091 (5)0.015 (3)0.005 (4)0.029 (4)
O20.055 (4)0.082 (5)0.106 (6)0.016 (4)0.016 (4)0.049 (4)
N10.042 (3)0.046 (3)0.034 (3)−0.003 (3)0.004 (2)−0.003 (3)
N20.035 (3)0.049 (3)0.036 (3)0.003 (3)0.000 (2)−0.001 (2)
C10.039 (4)0.064 (4)0.039 (3)−0.007 (3)−0.002 (3)−0.005 (4)
C20.033 (4)0.069 (5)0.047 (4)−0.006 (3)0.001 (3)−0.010 (3)
C30.044 (4)0.047 (4)0.047 (4)0.006 (3)−0.004 (3)−0.011 (3)
C40.032 (3)0.053 (4)0.045 (4)0.001 (3)−0.006 (3)−0.004 (3)
C50.048 (5)0.055 (4)0.067 (10)0.002 (4)−0.011 (5)0.012 (5)
C60.052 (5)0.059 (5)0.067 (5)0.000 (4)−0.008 (4)0.012 (4)
C70.044 (4)0.048 (4)0.043 (4)−0.003 (3)0.004 (3)−0.001 (3)
C80.050 (5)0.052 (4)0.043 (4)−0.004 (3)−0.001 (3)0.007 (3)
C90.037 (4)0.062 (5)0.038 (4)−0.011 (3)0.001 (3)−0.007 (3)
C100.047 (5)0.042 (4)0.042 (4)0.005 (3)−0.007 (3)−0.001 (3)
C110.043 (4)0.042 (4)0.038 (3)0.000 (3)−0.002 (3)−0.009 (3)
C120.039 (4)0.040 (3)0.045 (3)0.000 (3)−0.009 (3)−0.002 (3)

Geometric parameters (Å, °)

Hg—N12.439 (7)C3—H30.9500
Hg—N22.512 (6)C4—C121.401 (11)
Hg—Cl12.5270 (19)C4—C51.487 (15)
O1—C51.203 (11)C5—C61.572 (14)
O2—C61.206 (11)C6—C71.483 (12)
N1—C11.332 (10)C7—C111.386 (12)
N1—C121.344 (10)C7—C81.387 (12)
N2—C111.330 (10)C8—C91.392 (12)
N2—C101.331 (10)C8—H80.9500
C1—C21.393 (12)C9—C101.380 (11)
C1—H10.9500C9—H90.9500
C2—C31.374 (13)C10—H100.9500
C2—H20.9500C11—C121.516 (11)
C3—C41.384 (11)
N1—Hg—N1i146.8 (3)C4—C3—H3120.1
N1—Hg—N2i87.6 (2)C3—C4—C12118.4 (8)
N1i—Hg—N2i66.9 (2)C3—C4—C5120.1 (7)
N1—Hg—N266.9 (2)C12—C4—C5121.4 (7)
N1i—Hg—N287.6 (2)O1—C5—C4122.8 (9)
N2i—Hg—N281.0 (3)O1—C5—C6119.8 (11)
N1—Hg—Cl1106.71 (16)C4—C5—C6117.4 (8)
N1i—Hg—Cl193.95 (16)O2—C6—C7124.1 (9)
N2i—Hg—Cl1159.31 (13)O2—C6—C5118.3 (9)
N2—Hg—Cl190.78 (14)C7—C6—C5117.5 (8)
N1—Hg—Cl1i93.95 (16)C11—C7—C8119.4 (8)
N1i—Hg—Cl1i106.71 (16)C11—C7—C6122.0 (7)
N2i—Hg—Cl1i90.78 (14)C8—C7—C6118.6 (8)
N2—Hg—Cl1i159.31 (13)C7—C8—C9117.9 (8)
Cl1—Hg—Cl1i102.75 (10)C7—C8—H8121.0
C1—N1—C12118.3 (7)C9—C8—H8121.0
C1—N1—Hg121.4 (5)C10—C9—C8118.6 (7)
C12—N1—Hg120.0 (5)C10—C9—H9120.7
C11—N2—C10118.1 (7)C8—C9—H9120.7
C11—N2—Hg118.3 (5)N2—C10—C9123.5 (7)
C10—N2—Hg123.4 (5)N2—C10—H10118.3
N1—C1—C2123.3 (8)C9—C10—H10118.3
N1—C1—H1118.4N2—C11—C7122.5 (7)
C2—C1—H1118.4N2—C11—C12116.7 (7)
C3—C2—C1118.2 (7)C7—C11—C12120.8 (7)
C3—C2—H2120.9N1—C12—C4122.0 (8)
C1—C2—H2120.9N1—C12—C11117.3 (7)
C2—C3—C4119.8 (7)C4—C12—C11120.7 (7)
C2—C3—H3120.1
N1i—Hg—N1—C1135.2 (6)C4—C5—C6—C72.9 (16)
N2i—Hg—N1—C196.6 (6)O2—C6—C7—C11177.0 (10)
N2—Hg—N1—C1177.8 (6)C5—C6—C7—C11−2.3 (14)
Cl1—Hg—N1—C1−98.6 (6)O2—C6—C7—C8−2.6 (15)
Cl1i—Hg—N1—C15.9 (6)C5—C6—C7—C8178.0 (9)
N1i—Hg—N1—C12−50.0 (5)C11—C7—C8—C92.5 (12)
N2i—Hg—N1—C12−88.6 (6)C6—C7—C8—C9−177.8 (8)
N2—Hg—N1—C12−7.4 (5)C7—C8—C9—C10−2.2 (12)
Cl1—Hg—N1—C1276.2 (6)C11—N2—C10—C92.3 (12)
Cl1i—Hg—N1—C12−179.2 (5)Hg—N2—C10—C9−172.5 (6)
N1—Hg—N2—C117.4 (5)C8—C9—C10—N2−0.2 (12)
N1i—Hg—N2—C11165.7 (5)C10—N2—C11—C7−1.9 (11)
N2i—Hg—N2—C1198.7 (5)Hg—N2—C11—C7173.2 (6)
Cl1—Hg—N2—C11−100.4 (5)C10—N2—C11—C12177.9 (7)
Cl1i—Hg—N2—C1130.9 (8)Hg—N2—C11—C12−7.0 (8)
N1—Hg—N2—C10−177.7 (6)C8—C7—C11—N2−0.5 (12)
N1i—Hg—N2—C10−19.5 (6)C6—C7—C11—N2179.8 (8)
N2i—Hg—N2—C10−86.5 (6)C8—C7—C11—C12179.7 (7)
Cl1—Hg—N2—C1074.4 (6)C6—C7—C11—C120.0 (12)
Cl1i—Hg—N2—C10−154.2 (5)C1—N1—C12—C40.1 (11)
C12—N1—C1—C2−0.6 (12)Hg—N1—C12—C4−174.9 (5)
Hg—N1—C1—C2174.3 (6)C1—N1—C12—C11−178.1 (6)
N1—C1—C2—C3−0.5 (12)Hg—N1—C12—C116.9 (9)
C1—C2—C3—C42.2 (12)C3—C4—C12—N11.6 (11)
C2—C3—C4—C12−2.7 (11)C5—C4—C12—N1−179.4 (9)
C2—C3—C4—C5178.2 (9)C3—C4—C12—C11179.8 (7)
C3—C4—C5—O1−2.1 (18)C5—C4—C12—C11−1.2 (13)
C12—C4—C5—O1178.8 (11)N2—C11—C12—N10.3 (10)
C3—C4—C5—C6177.9 (9)C7—C11—C12—N1−179.9 (7)
C12—C4—C5—C6−1.1 (16)N2—C11—C12—C4−178.0 (7)
O1—C5—C6—O23.5 (19)C7—C11—C12—C41.9 (11)
C4—C5—C6—O2−176.5 (10)O1—C5—C6—O23.5 (19)
O1—C5—C6—C7−177.1 (11)

Symmetry codes: (i) −x, −y, z.

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2···Cl1ii0.952.693.578 (8)156
C9—H9···Cl1iii0.952.783.701 (8)164

Symmetry codes: (ii) x−1, y, z; (iii) x+1/2, y, z−1/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HY2254).

References

  • Alencastro, R. B. de, Bomfim, J. A. S., Filgueiras, C. A. L., Howie, R. A. & Wardell, J. L. (2005). Appl. Organomet. Chem. 19, 479–487.
  • Brandenburg, K. (1999). DIAMOND. Crystal Impact GbR, Bonn, Germany.
  • Flack, H. D. (1983). Acta Cryst. A39, 876–881.
  • Hooft, R. W. W. (1998). COLLECT. Nonius BV, Delft, The Netherlands.
  • Otwinowski, Z. & Minor, W. (1997). Methods in Enzymology, Vol. 276, Macromolecular Crystallography, Part A, edited by C. W. Carter Jr & R. M. Sweet, pp. 307–326. New York: Academic Press.
  • Ramezanipour, F., Aghabozorg, H. & Soleimannejad, J. (2005). Acta Cryst. E61, m1194–m1196.
  • Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Westrip, S. P. (2009). publCIF. In preparation.
  • Yamada, M., Tanaka, Y., Yashimoto, Y., Juroda, S. & Shimao, I. (1992). Bull. Chem. Soc. Jpn, 65, 1006–1011.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography