Acta Cryst. (2009). E65, m1448 [ doi:10.1107/S1600536809043529 ]
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C1)mercury(II)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).
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.
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.
Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).
![[Figure 1]](./hb5153fig1thm.gif)
| Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level. |
![[Figure 2]](./hb5153fig2thm.gif)
| 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. |
| [Hg(C7H5O2)Cl] | F(000) = 640 |
| Mr = 357.15 | Dx = 2.882 Mg m−3 |
| Monoclinic, P21/c | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2ybc | Cell parameters from 2640 reflections |
| a = 4.1004 (10) Å | θ = 2.7–29.5° |
| b = 14.842 (3) Å | µ = 18.97 mm−1 |
| c = 14.116 (3) Å | T = 295 K |
| β = 106.657 (6)° | Block, colorless |
| V = 823.0 (3) Å3 | 0.20 × 0.18 × 0.16 mm |
| Z = 4 |
| Bruker SMART CCD diffractometer | 1424 independent reflections |
| Radiation source: fine-focus sealed tube | 1333 reflections with I > 2σ(I) |
| graphite | Rint = 0.039 |
| φ and ω scans | θmax = 25.1°, θmin = 1.4° |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | h = −4→4 |
| Tmin = 0.116, Tmax = 0.151 | k = −12→17 |
| 4116 measured reflections | l = −16→15 |
| 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)] = 0.039 | Hydrogen site location: inferred from neighbouring sites |
| wR(F2) = 0.103 | H-atom parameters constrained |
| S = 1.09 | w = 1/[σ2(Fo2) + (0.0429P)2 + 12.0653P] where P = (Fo2 + 2Fc2)/3 |
| 1424 reflections | (Δ/σ)max = 0.001 |
| 101 parameters | Δρmax = 2.05 e Å−3 |
| 0 restraints | Δρmin = −1.73 e Å−3 |
| [Hg(C7H5O2)Cl] | V = 823.0 (3) Å3 |
| Mr = 357.15 | Z = 4 |
| Monoclinic, P21/c | Mo Kα radiation |
| a = 4.1004 (10) Å | µ = 18.97 mm−1 |
| b = 14.842 (3) Å | T = 295 K |
| c = 14.116 (3) Å | 0.20 × 0.18 × 0.16 mm |
| β = 106.657 (6)° |
| Bruker SMART CCD diffractometer | 1424 independent reflections |
| Absorption correction: multi-scan (SADABS; Sheldrick, 1996) | 1333 reflections with I > 2σ(I) |
| Tmin = 0.116, Tmax = 0.151 | Rint = 0.039 |
| 4116 measured reflections | θmax = 25.1° |
| R[F2 > 2σ(F2)] = 0.039 | w = 1/[σ2(Fo2) + (0.0429P)2 + 12.0653P] where P = (Fo2 + 2Fc2)/3 |
| wR(F2) = 0.103 | Δρmax = 2.05 e Å−3 |
| S = 1.09 | Δρmin = −1.73 e Å−3 |
| 1424 reflections | Absolute structure: ? |
| 101 parameters | Flack parameter: ? |
| 0 restraints | Rogers parameter: ? |
| H-atom parameters constrained |
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 | 0.32843 (16) | 0.87897 (3) | 0.53385 (4) | 0.0345 (2) | |
| Cl1 | 0.5374 (10) | 0.9140 (2) | 0.4016 (3) | 0.0405 (8) | |
| O1 | 0.093 (5) | 1.0269 (8) | 0.8767 (9) | 0.076 (4) | |
| O2 | 0.069 (4) | 0.6993 (7) | 0.5877 (8) | 0.055 (3) | |
| H2 | 0.0023 | 0.6493 | 0.5982 | 0.083* | |
| C1 | 0.031 (5) | 0.8833 (8) | 0.8033 (11) | 0.038 (3) | |
| C2 | 0.131 (4) | 0.9074 (9) | 0.7223 (10) | 0.033 (3) | |
| H2A | 0.1898 | 0.9671 | 0.7153 | 0.040* | |
| C3 | 0.148 (4) | 0.8460 (9) | 0.6511 (9) | 0.029 (3) | |
| C4 | 0.052 (4) | 0.7564 (10) | 0.6613 (10) | 0.036 (3) | |
| C5 | −0.063 (5) | 0.7317 (9) | 0.7410 (11) | 0.042 (3) | |
| H5 | −0.1288 | 0.6724 | 0.7467 | 0.051* | |
| C6 | −0.081 (4) | 0.7932 (10) | 0.8110 (10) | 0.039 (4) | |
| H6 | −0.1642 | 0.7766 | 0.8631 | 0.047* | |
| C7 | −0.007 (6) | 0.9495 (12) | 0.8760 (11) | 0.059 (5) | |
| H7 | −0.1119 | 0.9319 | 0.9235 | 0.070* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| Hg1 | 0.0437 (3) | 0.0258 (3) | 0.0364 (3) | −0.0009 (2) | 0.0153 (3) | 0.0038 (2) |
| Cl1 | 0.050 (2) | 0.0390 (18) | 0.0357 (17) | −0.0049 (17) | 0.0181 (16) | −0.0012 (15) |
| O1 | 0.133 (14) | 0.035 (6) | 0.067 (8) | −0.005 (8) | 0.040 (9) | −0.009 (6) |
| O2 | 0.099 (11) | 0.028 (5) | 0.047 (6) | −0.014 (6) | 0.033 (7) | −0.007 (5) |
| C1 | 0.050 (10) | 0.022 (7) | 0.043 (8) | 0.011 (6) | 0.015 (7) | 0.002 (5) |
| C2 | 0.036 (8) | 0.021 (6) | 0.044 (8) | 0.008 (6) | 0.013 (6) | 0.008 (6) |
| C3 | 0.032 (7) | 0.021 (6) | 0.030 (7) | 0.002 (6) | 0.003 (5) | 0.007 (5) |
| C4 | 0.042 (8) | 0.030 (7) | 0.029 (7) | −0.003 (6) | 0.002 (6) | 0.003 (6) |
| C5 | 0.061 (10) | 0.021 (6) | 0.047 (8) | −0.005 (7) | 0.020 (8) | 0.008 (6) |
| C6 | 0.052 (9) | 0.034 (8) | 0.034 (7) | −0.005 (7) | 0.014 (7) | 0.016 (6) |
| C7 | 0.096 (15) | 0.048 (10) | 0.038 (9) | 0.017 (10) | 0.027 (10) | 0.009 (7) |
| Hg1—C3 | 2.058 (13) | C2—C3 | 1.37 (2) |
| Hg1—Cl1 | 2.326 (4) | C2—H2A | 0.9300 |
| O1—C7 | 1.22 (2) | C3—C4 | 1.405 (19) |
| O2—C4 | 1.357 (17) | C4—C5 | 1.39 (2) |
| O2—H2 | 0.8193 | C5—C6 | 1.36 (2) |
| C1—C2 | 1.37 (2) | C5—H5 | 0.9300 |
| C1—C6 | 1.428 (19) | C6—H6 | 0.9300 |
| C1—C7 | 1.46 (2) | C7—H7 | 0.9300 |
| C3—Hg1—Cl1 | 179.1 (4) | O2—C4—C3 | 115.9 (13) |
| C4—O2—H2 | 109.5 | C5—C4—C3 | 120.1 (13) |
| C2—C1—C6 | 119.2 (13) | C6—C5—C4 | 120.8 (13) |
| C2—C1—C7 | 121.9 (13) | C6—C5—H5 | 119.6 |
| C6—C1—C7 | 118.4 (15) | C4—C5—H5 | 119.6 |
| C1—C2—C3 | 121.8 (13) | C5—C6—C1 | 119.2 (13) |
| C1—C2—H2A | 119.1 | C5—C6—H6 | 120.4 |
| C3—C2—H2A | 119.1 | C1—C6—H6 | 120.4 |
| C2—C3—C4 | 118.7 (13) | O1—C7—C1 | 122.3 (17) |
| C2—C3—Hg1 | 122.4 (10) | O1—C7—H7 | 118.8 |
| C4—C3—Hg1 | 118.8 (10) | C1—C7—H7 | 118.8 |
| O2—C4—C5 | 123.9 (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—C4 | 1(2) | C4—C5—C6—C1 | −2(3) |
| C1—C2—C3—Hg1 | −175.8 (12) | C2—C1—C6—C5 | 4(2) |
| C2—C3—C4—O2 | 179.0 (14) | C7—C1—C6—C5 | 176.7 (16) |
| Hg1—C3—C4—O2 | −3.9 (18) | C2—C1—C7—O1 | −11 (3) |
| C2—C3—C4—C5 | 1(2) | C6—C1—C7—O1 | 177.2 (19) |
| Hg1—C3—C4—C5 | 178.5 (12) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O1i | 0.82 | 1.91 | 2.727 (16) | 172 |
| Symmetry codes: (i) −x, y−1/2, −z+3/2. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| O2—H2···O1i | 0.82 | 1.91 | 2.727 (16) | 172 |
| Symmetry codes: (i) −x, y−1/2, −z+3/2. |
Dupont, J., Consorti, C. S. & Spencer, J. (2005). Chem. Rev. 105, 2527–2571.
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.
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.
Spek, A. L. (2009). Acta Cryst. D65, 148–155.
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.
Xu, C., Cen, F.-F., Wang, Z.-Q. & Zhang, Y.-Q. (2009). Acta Cryst. E65, m754.
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).