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Acta Crystallogr Sect E Struct Rep Online. 2009 November 1; 65(Pt 11): m1448.
Published online 2009 October 28. doi:  10.1107/S1600536809043529
PMCID: PMC2971446

Chlorido(5-formyl-2-hydroxy­phenyl-κC 1)mercury(II)

Abstract

In the planar (r.m.s. deviation = 0.027 Å) title compound, [Hg(C7H5O2)Cl], the HgII atom shows a typical linear coordination by a C atom of the benzene ring and a Cl atom. Inter­molecular O—H(...)O hydrogen bonds are present in the crystal structure, resulting in chains propagating along the b axis. The crystal studied was a non-merohedral twin, with a twin ratio of 0.802 (2):0.198 (2).

Related literature

For general background to the use of cyclo­metallated compounds in synthesis, catalysis and materials, see: Gruter et al. (1995 [triangle]); Dupont et al. (2005 [triangle]). For related structures and the synthesis of related cyclo­mercurated compounds, see: Xu et al. (2009 [triangle]). For the preparation of cyclo­mercurated compounds, see: Ryabov et al. (2003 [triangle]); Wu et al. (2001 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-65-m1448-scheme1.jpg

Experimental

Crystal data

  • [Hg(C7H5O2)Cl]
  • M r = 357.15
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-65-m1448-efi1.jpg
  • a = 4.1004 (10) Å
  • b = 14.842 (3) Å
  • c = 14.116 (3) Å
  • β = 106.657 (6)°
  • V = 823.0 (3) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 18.97 mm−1
  • T = 295 K
  • 0.20 × 0.18 × 0.16 mm

Data collection

  • Bruker SMART CCD diffractometer
  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996 [triangle]) T min = 0.116, T max = 0.151
  • 4116 measured reflections
  • 1424 independent reflections
  • 1333 reflections with I > 2σ(I)
  • R int = 0.039

Refinement

  • R[F 2 > 2σ(F 2)] = 0.039
  • wR(F 2) = 0.103
  • S = 1.09
  • 1424 reflections
  • 101 parameters
  • H-atom parameters constrained
  • Δρmax = 2.05 e Å−3
  • Δρmin = −1.73 e Å−3

Data collection: SMART (Siemens, 1996 [triangle]); cell refinement: SAINT (Siemens, 1996 [triangle]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 [triangle]).

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

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809043529/hb5153sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809043529/hb5153Isup2.hkl

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

supplementary crystallographic information

Comment

Cyclometallated compounds have attracted much research interest owing to theirs utility in synthesis, catalysis and materials (Gruter et al., 1995; Dupont et al., 2005). Among them, cyclomercurated compounds are easy to prepare through a C–H activation process and are stable but reasonably reactive (Wu et al., 2001; Ryabov et al., 2003).

In the planar title compound (Fig. 1), the mercury(II) atom shows a typical linear coordination geometry with a carbon atom of the benzene ring and the chloride atom in trans position. O2–Hg1 distance (3.047 (2) Å) is much longer than those of the related Hg(II) complex (Xu et al., 2009). The C–Hg and Hg–Cl bond distances are within normal ranges. The C3–Hg1–Cl1 angle is 179.1 (4) °. Intermolecular O—H···O hydrogen bonds are present in the crystal structure (Table 1), resulting in a one-dimensional supramolecular architecture (Fig.2).

Experimental

The title compound was prepared from the p-hydroxybenzaldehyde with Hg(OAc)2 and subsequent treatment with LiCl and recrystallized from dichloromethane-petroleum ether solution at room temperature to give (I) as colorless crystals suitable for single-crystal X-ray diffraction.

Refinement

All H atoms were placed in geometrically idealized positions, with C—H = 0.93–0.96 Å, O—H = 0.82–0.85 Å and N—H = 0.86 Å. Uiso(H) = 1.2Ueq(C,N), and 1.5Ueq(O).

The structure is a non-merohdral twin. The twin law, as given by PLATON (Spek, 2009), is (-1 0 0, 0 - 1 0, 2 0 1), which lowered the R1 index from 0.116 to 0.039.

Figures

Fig. 1.
The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level.
Fig. 2.
Partial view of the crystal packing showing the formation of the one-dimensional chain structure formed by the intermolecular O—H···O hydrogen bonds.

Crystal data

[Hg(C7H5O2)Cl]F(000) = 640
Mr = 357.15Dx = 2.882 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 2640 reflections
a = 4.1004 (10) Åθ = 2.7–29.5°
b = 14.842 (3) ŵ = 18.97 mm1
c = 14.116 (3) ÅT = 295 K
β = 106.657 (6)°Block, colorless
V = 823.0 (3) Å30.20 × 0.18 × 0.16 mm
Z = 4

Data collection

Bruker SMART CCD diffractometer1424 independent reflections
Radiation source: fine-focus sealed tube1333 reflections with I > 2σ(I)
graphiteRint = 0.039
[var phi] and ω scansθmax = 25.1°, θmin = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)h = −4→4
Tmin = 0.116, Tmax = 0.151k = −12→17
4116 measured reflectionsl = −16→15

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.039Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.103H-atom parameters constrained
S = 1.09w = 1/[σ2(Fo2) + (0.0429P)2 + 12.0653P] where P = (Fo2 + 2Fc2)/3
1424 reflections(Δ/σ)max = 0.001
101 parametersΔρmax = 2.05 e Å3
0 restraintsΔρmin = −1.73 e Å3

Special details

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)

xyzUiso*/Ueq
Hg10.32843 (16)0.87897 (3)0.53385 (4)0.0345 (2)
Cl10.5374 (10)0.9140 (2)0.4016 (3)0.0405 (8)
O10.093 (5)1.0269 (8)0.8767 (9)0.076 (4)
O20.069 (4)0.6993 (7)0.5877 (8)0.055 (3)
H20.00230.64930.59820.083*
C10.031 (5)0.8833 (8)0.8033 (11)0.038 (3)
C20.131 (4)0.9074 (9)0.7223 (10)0.033 (3)
H2A0.18980.96710.71530.040*
C30.148 (4)0.8460 (9)0.6511 (9)0.029 (3)
C40.052 (4)0.7564 (10)0.6613 (10)0.036 (3)
C5−0.063 (5)0.7317 (9)0.7410 (11)0.042 (3)
H5−0.12880.67240.74670.051*
C6−0.081 (4)0.7932 (10)0.8110 (10)0.039 (4)
H6−0.16420.77660.86310.047*
C7−0.007 (6)0.9495 (12)0.8760 (11)0.059 (5)
H7−0.11190.93190.92350.070*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
Hg10.0437 (3)0.0258 (3)0.0364 (3)−0.0009 (2)0.0153 (3)0.0038 (2)
Cl10.050 (2)0.0390 (18)0.0357 (17)−0.0049 (17)0.0181 (16)−0.0012 (15)
O10.133 (14)0.035 (6)0.067 (8)−0.005 (8)0.040 (9)−0.009 (6)
O20.099 (11)0.028 (5)0.047 (6)−0.014 (6)0.033 (7)−0.007 (5)
C10.050 (10)0.022 (7)0.043 (8)0.011 (6)0.015 (7)0.002 (5)
C20.036 (8)0.021 (6)0.044 (8)0.008 (6)0.013 (6)0.008 (6)
C30.032 (7)0.021 (6)0.030 (7)0.002 (6)0.003 (5)0.007 (5)
C40.042 (8)0.030 (7)0.029 (7)−0.003 (6)0.002 (6)0.003 (6)
C50.061 (10)0.021 (6)0.047 (8)−0.005 (7)0.020 (8)0.008 (6)
C60.052 (9)0.034 (8)0.034 (7)−0.005 (7)0.014 (7)0.016 (6)
C70.096 (15)0.048 (10)0.038 (9)0.017 (10)0.027 (10)0.009 (7)

Geometric parameters (Å, °)

Hg1—C32.058 (13)C2—C31.37 (2)
Hg1—Cl12.326 (4)C2—H2A0.9300
O1—C71.22 (2)C3—C41.405 (19)
O2—C41.357 (17)C4—C51.39 (2)
O2—H20.8193C5—C61.36 (2)
C1—C21.37 (2)C5—H50.9300
C1—C61.428 (19)C6—H60.9300
C1—C71.46 (2)C7—H70.9300
C3—Hg1—Cl1179.1 (4)O2—C4—C3115.9 (13)
C4—O2—H2109.5C5—C4—C3120.1 (13)
C2—C1—C6119.2 (13)C6—C5—C4120.8 (13)
C2—C1—C7121.9 (13)C6—C5—H5119.6
C6—C1—C7118.4 (15)C4—C5—H5119.6
C1—C2—C3121.8 (13)C5—C6—C1119.2 (13)
C1—C2—H2A119.1C5—C6—H6120.4
C3—C2—H2A119.1C1—C6—H6120.4
C2—C3—C4118.7 (13)O1—C7—C1122.3 (17)
C2—C3—Hg1122.4 (10)O1—C7—H7118.8
C4—C3—Hg1118.8 (10)C1—C7—H7118.8
O2—C4—C5123.9 (13)
C6—C1—C2—C3−4(2)O2—C4—C5—C6−178.4 (16)
C7—C1—C2—C3−176.1 (16)C3—C4—C5—C6−1(2)
C1—C2—C3—C41(2)C4—C5—C6—C1−2(3)
C1—C2—C3—Hg1−175.8 (12)C2—C1—C6—C54(2)
C2—C3—C4—O2179.0 (14)C7—C1—C6—C5176.7 (16)
Hg1—C3—C4—O2−3.9 (18)C2—C1—C7—O1−11 (3)
C2—C3—C4—C51(2)C6—C1—C7—O1177.2 (19)
Hg1—C3—C4—C5178.5 (12)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
O2—H2···O1i0.821.912.727 (16)172

Symmetry codes: (i) −x, y−1/2, −z+3/2.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: HB5153).

References

  • Dupont, J., Consorti, C. S. & Spencer, J. (2005). Chem. Rev.105, 2527–2571. [PubMed]
  • Gruter, G. M., Van Klink, G. P. M., Akkerman, O. S. & Bickelhaupt, F. (1995). Chem. Rev.95, 2405–2456.
  • Ryabov, A. D., Soukharev, V. S., Alexandrova, L., Lagadec, R. L. & Pfeffer, M. (2003). Inorg. Chem.42, 6598–6600. [PubMed]
  • Sheldrick, G. M. (1996). SADABS University of Göttingen, Germany.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Siemens (1996). SMART and SAINT Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
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  • Wu, Y. J., Huo, S. Q., Gong, J. F., Cui, X. L., Ding, K. L., Du, C. X., Liu, Y. H. & Song, M. P. (2001). J. Organomet. Chem.637–639, 27–46.
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