Chlorido(2-formyl-6-hydroxy­phenyl-κC1)mercury(II)

Xu, C.; Cen, F.-F.; Wang, Z.-Q.; Zhang, Y.-Q.

doi:10.1107/S160053680902145X

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 7| July 2009| Page m754

doi:10.1107/S160053680902145X

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Chlorido(2-formyl-6-hydroxyphenyl-κC¹)mercury(II)

Chen Xu,^a ^* Fei-Fei Cen,^b Zhi-Qiang Wang ^a and Yu-Qing Zhang ^b

^aCollege of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang 471022, People's Republic of China, and ^bChemical Engineering and Pharmaceutics School, Henan University of Science and Technology, Luoyang 471003, People's Republic of China
^*Correspondence e-mail: xubohan@163.com

(Received 1 June 2009; accepted 5 June 2009; online 10 June 2009)

In the planar [r.m.s. deviation 0.0265 Å] title compound, [Hg(C₇H₅O₂)Cl], the Hg^II atom shows a typical linear coordination by a C atom of a benzene ring and a Cl atom. The benzene C atom and the aldehyde O atom chelate the Hg^II atom by assuming the Hg⋯O separation of 2.817 (9) Å as a weak intramolecular coordination bonding distance. The resulting five-membered metallacycle is nearly coplanar with the benzene ring dihedral angle 2.9 (1)°]. Intermolecular O—H⋯O hydrogen bonds are present in the crystal structure, resulting in a one-dimensional supramolecular architecture parallel to [201].

Related literature

For historical background and for properties of cyclometallated compounds, see: Dupont et al. (2005 ); Xu et al. (2009 ). For the properties of cyclomercurated compounds, see: Wu et al. (2001 ); Ryabov et al. (2003 ). For related structure, see: King et al. (2002 ); Zhou et al. (2005 ); Hao et al. (2007 ).

Experimental

Crystal data

[Hg(C₇H₅O₂)Cl]
M_r = 357.15
Monoclinic, P 2₁ /c
a = 4.7200 (19) Å
b = 17.702 (7) Å
c = 10.506 (4) Å
β = 98.839 (5)°
V = 867.4 (6) Å³
Z = 4
Mo Kα radiation
μ = 18.00 mm⁻¹
T = 296 K
0.08 × 0.01 × 0.01 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.327, T_max = 0.841
5002 measured reflections
1595 independent reflections
1130 reflections with I > 2σ(I)
R_int = 0.050

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.114
S = 1.01
1595 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 0.94 e Å⁻³
Δρ_min = −2.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O2ⁱ	0.82	1.93	2.730 (12)	165
Symmetry code: (i) $[x-1, -y+{\script{3\over 2}}, z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680902145X/si2180sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S160053680902145X/si2180Isup2.hkl

checkCIF report

Comment top

Cyclometallated compounds containing a metal-carbon bond stabilized by the intramolecular coordination of one or two neutral atoms have a very rich chemistry and are widely used in synthesis, catalysis and materials (Dupont et al., 2005; Xu et al., 2009). Among them, cyclomercurated compounds are easy to prepare through a C—H activation process and their ease in undergoing transmetallation for the synthesis of other organometallic compounds (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 (2.817 (9) Å) is shorter than the sum of van der Waals radii (3.29 Å)of Hg and O (King et al., 2002), indicating the presence of the weak intramolecular coordination, while it is longer than those of the related Hg(II) complex (Zhou et al., 2005). The C—Hg and Hg—Cl bond distances are within normal ranges. The C7—Hg1—Cl1 angle is 178.1 (3)°, slightly smaller than the ideal value of 180° in organic derivatives of mercury(Hao et al., 2007). Intermolecular O—H···O hydrogen bonds are present in the crystal structure (Table 1), resulting in a one-dimensional supramolecular architecture (Fig.2).

Related literature top

For historical background and for properties of cyclometallated compounds, see: Dupont et al. (2005); Xu et al. (2009). For the properties of cyclomercurated compounds, see: Wu et al. (2001); Ryabov et al. (2003). For related structure, see: King et al. (2002); Zhou et al. (2005); Hao et al. (2007).

Experimental top

The title compound was prepared from the m-hydroxybenzaldehyde with Hg(OAc)₂ and subsequent treatment with LiCl and recrystallized from dichloromethane-petroleum ether solution at room temperature to give the desired product as colorless crystals suitable for single-crystal X-ray diffraction (yield 82%; m.p 442–444 K). IR data (v_max/ cm^-1): 3408, 2926, 1651, 1567, 1445, 1291, 1199, 789. NMR δ(H) 7.18(1H,d), 7.45 (1H,t), 7.52(1H,d), 10.12(1H,s), 12.11(1H,m).

Computing details top

Data collection: SMART (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); 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).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids 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.

Chlorido(2-formyl-6-hydroxyphenyl-κC¹)mercury(II) top

Crystal data top

[Hg(C₇H₅O₂)Cl]	F(000) = 640
M_r = 357.15	D_x = 2.735 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 4.7200 (19) Å	Cell parameters from 1175 reflections
b = 17.702 (7) Å	θ = 2.3–22.3°
c = 10.506 (4) Å	µ = 18.00 mm⁻¹
β = 98.839 (5)°	T = 296 K
V = 867.4 (6) Å³	Block, colourless
Z = 4	0.08 × 0.01 × 0.01 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1595 independent reflections
Radiation source: fine-focus sealed tube	1130 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.050
ϕ and ω scans	θ_max = 25.5°, θ_min = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −5→5
T_min = 0.327, T_max = 0.841	k = −21→21
5002 measured reflections	l = −12→12

Refinement top

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.114	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0564P)² + 3.2348P] where P = (F_o² + 2F_c²)/3
1595 reflections	(Δ/σ)_max = 0.001
101 parameters	Δρ_max = 0.94 e Å⁻³
0 restraints	Δρ_min = −2.32 e Å⁻³

Crystal data top

[Hg(C₇H₅O₂)Cl]	V = 867.4 (6) Å³
M_r = 357.15	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 4.7200 (19) Å	µ = 18.00 mm⁻¹
b = 17.702 (7) Å	T = 296 K
c = 10.506 (4) Å	0.08 × 0.01 × 0.01 mm
β = 98.839 (5)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	1595 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1130 reflections with I > 2σ(I)
T_min = 0.327, T_max = 0.841	R_int = 0.050
5002 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.114	H-atom parameters constrained
S = 1.01	Δρ_max = 0.94 e Å⁻³
1595 reflections	Δρ_min = −2.32 e Å⁻³
101 parameters

Special details top

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) top

	x	y	z	U_iso*/U_eq
Hg1	0.26063 (12)	0.66539 (3)	0.30597 (6)	0.0470 (2)
O1	−0.160 (2)	0.6917 (5)	0.5036 (10)	0.050 (2)
H1	−0.2948	0.6960	0.5439	0.074*
O2	0.468 (2)	0.7878 (5)	0.1758 (9)	0.052 (2)
Cl1	0.4684 (11)	0.5580 (2)	0.2416 (5)	0.0833 (14)
C1	0.345 (3)	0.8403 (7)	0.2208 (14)	0.043 (3)
H1A	0.3802	0.8888	0.1928	0.052*
C2	0.151 (3)	0.8330 (7)	0.3132 (13)	0.042 (3)
C3	0.039 (3)	0.8998 (7)	0.3574 (14)	0.051 (4)
H3	0.0837	0.9460	0.3235	0.061*
C4	−0.137 (3)	0.8974 (7)	0.4509 (13)	0.048 (4)
H4	−0.2123	0.9420	0.4788	0.058*
C5	−0.204 (3)	0.8276 (7)	0.5043 (13)	0.044 (3)
H5	−0.3193	0.8257	0.5683	0.053*
C6	−0.092 (3)	0.7611 (7)	0.4591 (12)	0.042 (3)
C7	0.087 (2)	0.7635 (7)	0.3644 (11)	0.032 (3)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.0477 (4)	0.0392 (3)	0.0583 (4)	0.0027 (3)	0.0213 (3)	−0.0048 (3)
O1	0.047 (6)	0.048 (5)	0.060 (6)	−0.006 (4)	0.027 (5)	0.003 (5)
O2	0.047 (6)	0.058 (6)	0.056 (6)	−0.003 (5)	0.028 (5)	−0.011 (5)
Cl1	0.098 (4)	0.044 (2)	0.117 (4)	0.016 (2)	0.045 (3)	−0.010 (2)
C1	0.033 (7)	0.043 (7)	0.054 (8)	−0.002 (6)	0.007 (6)	0.005 (7)
C2	0.029 (6)	0.053 (8)	0.043 (7)	−0.008 (6)	0.007 (6)	0.000 (6)
C3	0.058 (9)	0.034 (7)	0.070 (10)	0.012 (6)	0.038 (8)	0.012 (7)
C4	0.056 (9)	0.035 (7)	0.056 (9)	0.006 (6)	0.012 (7)	−0.010 (6)
C5	0.040 (8)	0.053 (8)	0.044 (8)	0.005 (7)	0.020 (6)	−0.007 (7)
C6	0.027 (7)	0.054 (8)	0.045 (8)	−0.012 (6)	0.007 (6)	0.000 (6)
C7	0.023 (6)	0.043 (7)	0.026 (6)	−0.004 (5)	−0.008 (5)	0.001 (5)

Geometric parameters (Å, º) top

Hg1—C7	2.052 (12)	C2—C3	1.403 (17)
Hg1—Cl1	2.288 (4)	C3—C4	1.382 (17)
O1—C6	1.370 (14)	C3—H3	0.9300
O1—H1	0.8200	C4—C5	1.412 (18)
O2—C1	1.229 (14)	C4—H4	0.9300
C1—C2	1.440 (18)	C5—C6	1.402 (17)
C1—H1A	0.9300	C5—H5	0.9300
C2—C7	1.394 (16)	C6—C7	1.403 (16)

C7—Hg1—Cl1	178.1 (3)	C3—C4—H4	119.9
C6—O1—H1	109.5	C5—C4—H4	119.9
O2—C1—C2	125.4 (12)	C6—C5—C4	118.9 (11)
O2—C1—H1A	117.3	C6—C5—H5	120.6
C2—C1—H1A	117.3	C4—C5—H5	120.6
C7—C2—C1	122.4 (12)	O1—C6—C7	117.8 (11)
C7—C2—C3	120.1 (12)	O1—C6—C5	121.2 (11)
C1—C2—C3	117.3 (11)	C7—C6—C5	121.0 (12)
C4—C3—C2	120.6 (12)	C2—C7—C6	119.2 (11)
C4—C3—H3	119.7	C2—C7—Hg1	120.8 (9)
C2—C3—H3	119.7	C6—C7—Hg1	119.9 (9)
C3—C4—C5	120.2 (11)

O2—C1—C2—C7	2 (2)	C3—C2—C7—C6	0.8 (19)
O2—C1—C2—C3	177.6 (14)	C1—C2—C7—Hg1	−1.9 (18)
C7—C2—C3—C4	−1 (2)	C3—C2—C7—Hg1	−177.8 (10)
C1—C2—C3—C4	−176.7 (14)	O1—C6—C7—C2	177.3 (12)
C2—C3—C4—C5	1 (2)	C5—C6—C7—C2	−1.1 (19)
C3—C4—C5—C6	−1 (2)	O1—C6—C7—Hg1	−4.2 (16)
C4—C5—C6—O1	−177.0 (12)	C5—C6—C7—Hg1	177.4 (10)
C4—C5—C6—C7	1 (2)	Cl1—Hg1—C7—C2	46 (10)
C1—C2—C7—C6	176.6 (12)	Cl1—Hg1—C7—C6	−132 (10)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.93	2.730 (12)	165

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

Experimental details

Crystal data
Chemical formula	[Hg(C₇H₅O₂)Cl]
M_r	357.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	296
a, b, c (Å)	4.7200 (19), 17.702 (7), 10.506 (4)
β (°)	98.839 (5)
V (Å³)	867.4 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	18.00
Crystal size (mm)	0.08 × 0.01 × 0.01

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.327, 0.841
No. of measured, independent and observed [I > 2σ(I)] reflections	5002, 1595, 1130
R_int	0.050
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.114, 1.01
No. of reflections	1595
No. of parameters	101
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.94, −2.32

Computer programs: SMART (Bruker, 2004), SAINT (Bruker, 2004), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O2ⁱ	0.82	1.93	2.730 (12)	164.8

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

Acknowledgements

This work was supported by the Natural Science Foundation of Henan Education Department (No. 2009B150019).

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