Chlorido(5-formyl-2-hydroxy­phenyl-κC1)mercury(II)

Zheng, Z.-B.; Ma, S.-Y.; Wu, R.-T.; Han, Y.-F.; Lu, J.-R.

doi:10.1107/S1600536809043529

metal-organic compounds

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Chlorido(5-formyl-2-hydroxyphenyl-κC¹)mercury(II)

Ze-Bao Zheng,^a ^* Shi-Ying Ma,^a Ren-Tao Wu,^a Yin-Feng Han ^a and Jing-Rong Lu ^a

^aDepartment of Chemistry and Environmental Science, Taishan University, 271021 Taian, Shandong, People's Republic of China
^*Correspondence e-mail: zhengzebao@163.com

(Received 19 October 2009; accepted 22 October 2009; online 28 October 2009)

In the planar (r.m.s. deviation = 0.027 Å) title compound, [Hg(C₇H₅O₂)Cl], the Hg^II 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 ); Dupont et al. (2005 ). For related structures and the synthesis of related cyclomercurated compounds, see: Xu et al. (2009 ). For the preparation of cyclomercurated compounds, see: Ryabov et al. (2003 ); Wu et al. (2001 ).

Experimental

Crystal data

[Hg(C₇H₅O₂)Cl]
M_r = 357.15
Monoclinic, P 2₁ /c
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 ) 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[F² > 2σ(F²)] = 0.039
wR(F²) = 0.103
S = 1.09
1424 reflections
101 parameters
H-atom parameters constrained
Δρ_max = 2.05 e Å⁻³
Δρ_min = −1.73 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Hg1—C3	2.058 (13)
Hg1—Cl1	2.326 (4)

C3—Hg1—Cl1	179.1 (4)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯O1ⁱ	0.82	1.91	2.727 (16)	172
Symmetry code: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); 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 and PLATON (Spek, 2009 ).

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536809043529/hb5153Isup2.hkl

checkCIF report

Comment top

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).

Related literature top

For general background to the use of cyclometallated compounds in synthesis, catalysis and materials, see: Gruter et al. (1995); Dupont et al., (2005). For related structures and the synthesis of related cyclomercurated compounds, see: Xu et al. (2009). For the preparation of cyclomercurated compounds through a C–H activation process, see: Ryabov et al. (2003); Wu et al. (2001).

Experimental top

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.

Structure description top

Computing details top

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).

Figures top

	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.

Chlorido(5-formyl-2-hydroxyphenyl-κC¹)mercury(II) top

Crystal data top

[Hg(C₇H₅O₂)Cl]	F(000) = 640
M_r = 357.15	D_x = 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

Data collection top

Bruker SMART CCD diffractometer	1424 independent reflections
Radiation source: fine-focus sealed tube	1333 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
φ and ω scans	θ_max = 25.1°, θ_min = 1.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −4→4
T_min = 0.116, T_max = 0.151	k = −12→17
4116 measured reflections	l = −16→15

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.103	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0429P)² + 12.0653P] where P = (F_o² + 2F_c²)/3
1424 reflections	(Δ/σ)_max = 0.001
101 parameters	Δρ_max = 2.05 e Å⁻³
0 restraints	Δρ_min = −1.73 e Å⁻³

Crystal data top

[Hg(C₇H₅O₂)Cl]	V = 823.0 (3) Å³
M_r = 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)°

Data collection top

Bruker SMART CCD diffractometer	1424 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1333 reflections with I > 2σ(I)
T_min = 0.116, T_max = 0.151	R_int = 0.039
4116 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.103	H-atom parameters constrained
S = 1.09	w = 1/[σ²(F_o²) + (0.0429P)² + 12.0653P] where P = (F_o² + 2F_c²)/3
1424 reflections	Δρ_max = 2.05 e Å⁻³
101 parameters	Δρ_min = −1.73 e Å⁻³

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	0.32843 (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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	1.91	2.727 (16)	172

Symmetry code: (i) −x, y−1/2, −z+3/2.

Experimental details

Crystal data
Chemical formula	[Hg(C₇H₅O₂)Cl]
M_r	357.15
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	295
a, b, c (Å)	4.1004 (10), 14.842 (3), 14.116 (3)
β (°)	106.657 (6)
V (Å³)	823.0 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	18.97
Crystal size (mm)	0.20 × 0.18 × 0.16

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.116, 0.151
No. of measured, independent and observed [I > 2σ(I)] reflections	4116, 1424, 1333
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.103, 1.09
No. of reflections	1424
No. of parameters	101
H-atom treatment	H-atom parameters constrained
	w = 1/[σ²(F_o²) + (0.0429P)² + 12.0653P] where P = (F_o² + 2F_c²)/3
Δρ_max, Δρ_min (e Å⁻³)	2.05, −1.73

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top

Hg1—C3	2.058 (13)	Hg1—Cl1	2.326 (4)

C3—Hg1—Cl1	179.1 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···O1ⁱ	0.82	1.91	2.727 (16)	172

Symmetry code: (i) −x, y−1/2, −z+3/2.

References

Dupont, J., Consorti, C. S. & Spencer, J. (2005). Chem. Rev. 105, 2527–2571. Web of Science CrossRef PubMed CAS Google Scholar
Gruter, G. M., Van Klink, G. P. M., Akkerman, O. S. & Bickelhaupt, F. (1995). Chem. Rev. 95, 2405–2456. CrossRef CAS Web of Science Google Scholar
Ryabov, A. D., Soukharev, V. S., Alexandrova, L., Lagadec, R. L. & Pfeffer, M. (2003). Inorg. Chem. 42, 6598–6600. Web of Science CSD CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
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. Web of Science CrossRef CAS Google Scholar
Xu, C., Cen, F.-F., Wang, Z.-Q. & Zhang, Y.-Q. (2009). Acta Cryst. E65, m754. Web of Science CSD CrossRef IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 11| November 2009| Page m1448

https://doi.org/10.1107/S1600536809043529

Open

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