catena-Poly[[bis­(pyridine-3-carb­oxy­lic acid-κN)mercury(II)]-di-μ-chlorido]

Shirvan, S.A.; Haydari Dezfuli, S.

doi:10.1107/S1600536812012986

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 4| April 2012| Page m516

doi:10.1107/S1600536812012986

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catena-Poly[[bis(pyridine-3-carboxylic acid-κN)mercury(II)]-di-μ-chlorido]

Sadif A. Shirvan ^a ^* and Sara Haydari Dezfuli ^a

^aDepartment of Chemistry, Omidieh Branch, Islamic Azad University, Omidieh, Iran
^*Correspondence e-mail: sadif_shirvan1@yahoo.com

(Received 19 March 2012; accepted 24 March 2012; online 31 March 2012)

In the title compound, [HgCl₂(C₆H₅NO₂)₂]_n, the Hg^II cation is located on an inversion center and is six-coordinated in a distorted octahedral geometry by two N atoms from two pyridine-3-carboxylic acid molecules and four bridging Cl⁻ anions. The bridging function of the Cl⁻ anions leads to polymeric chains running along the a axis. One Hg—Cl bond is much longer than the other. In the crystal, O—H⋯O and weak C—H⋯Cl hydrogen bonds are observed.

Related literature

For related structures, see: Lu & Kohler (2002 ); Liang & Li (2005 ); Zhang et al. (1996 ); Ghazzali et al. (2007 ); Lin et al. (1998 ); Cotton et al. (1991 ).

Experimental

Crystal data

[HgCl₂(C₆H₅NO₂)₂]
M_r = 517.71
Triclinic, $[P \overline 1]$
a = 3.8298 (5) Å
b = 6.5626 (9) Å
c = 14.5831 (18) Å
α = 98.001 (10)°
β = 95.315 (11)°
γ = 92.963 (11)°
V = 360.62 (8) Å³
Z = 1
Mo Kα radiation
μ = 11.06 mm⁻¹
T = 298 K
0.20 × 0.10 × 0.05 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.293, T_max = 0.523
4417 measured reflections
1917 independent reflections
1913 reflections with I > 2σ(I)
R_int = 0.078

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.082
S = 0.83
1917 reflections
98 parameters
H-atom parameters constrained
Δρ_max = 1.02 e Å⁻³
Δρ_min = −1.22 e Å⁻³

Table 1
Selected bond lengths (Å)

Hg1—Cl1	2.4608 (13)
Hg1—Cl1ⁱ	2.8790 (13)
Hg1—N1ⁱⁱ	2.519 (4)
Symmetry codes: (i) x-1, y, z; (ii) -x+1, -y+2, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2A⋯O1ⁱⁱⁱ	0.82	1.80	2.618 (7)	171
C1—H1⋯Cl1^iv	0.93	2.79	3.582 (6)	144
C6—H6⋯Cl1ⁱⁱ	0.93	2.78	3.454 (5)	130
Symmetry codes: (ii) -x+1, -y+2, -z+1; (iii) -x, -y+2, -z; (iv) -x+2, -y+1, -z+1.

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812012986/xu5491sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812012986/xu5491Isup2.hkl

checkCIF report

Comment top

3-Pyridine carboxylic acid (pyc), is a good ligand, and a few complexes with pyc have been prepared, such as that of cadmium (Lu & Kohler, 2002; Liang & Li, 2005; Zhang et al., 1996) and zinc (Ghazzali et al., 2007; Lin et al., 1998; Cotton et al., 1991). Here, we report the synthesis and structure of the title compound.

The asymmetric unit of the title compound, (Fig. 1), contains one half -molecule. The Hg^II atom is six-coordinated in a distorted octahedral configuration by two N atoms from two 3-pyridine carboxylic acid and four bridging Cl. The bridging function of the chloro atoms leads to a one-dimensional chain structure. The Hg—Cl and Hg—N bond lengths and angles are collected in Table 1.

In the crystal structure, intermolecular O—H···O and C—H···Cl hydrogen bonds (Table 2, Fig. 2) may stabilize the structure.

Related literature top

For related structures, see: Lu & Kohler (2002); Liang & Li (2005); Zhang et al. (1996); Ghazzali et al. (2007); Lin et al. (1998); Cotton et al. (1991).

Experimental top

A solution of pyridine-3-carboxylic acid (0.25 g, 2.0 mmol) in methanol (20 ml) was added to a solution of HgCl₂ (0.27 g, 1.0 mmol) in methanol (20 ml) and the resulting colorless solution was stirred for 15 min at room temperature. This solution was left to evaporate slowly at room temperature. After one week, colorless needle crystals of the title compound were isolated (yield 0.41 g, 79.2%).

Structure description top

In the crystal structure, intermolecular O—H···O and C—H···Cl hydrogen bonds (Table 2, Fig. 2) may stabilize the structure.

For related structures, see: Lu & Kohler (2002); Liang & Li (2005); Zhang et al. (1996); Ghazzali et al. (2007); Lin et al. (1998); Cotton et al. (1991).

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level. [Symmetry codes: (a) -1 + x,y,z; (c) 1 - x,2 - y,1 - z; (d) 2 - x,2 - y,1 - z].
	Fig. 2. A packing diagram of the title complex. Hydrogen bonds are shown as dashed lines.

catena-Poly[[bis(pyridine-3-carboxylic acid-κN)mercury(II)]-di-µ-chlorido] top

Crystal data top

[HgCl₂(C₆H₅NO₂)₂]	Z = 1
M_r = 517.71	F(000) = 242
Triclinic, P1	D_x = 2.384 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 3.8298 (5) Å	Cell parameters from 1010 reflections
b = 6.5626 (9) Å	θ = 2.8–29.2°
c = 14.5831 (18) Å	µ = 11.06 mm⁻¹
α = 98.001 (10)°	T = 298 K
β = 95.315 (11)°	Needle, colorless
γ = 92.963 (11)°	0.20 × 0.10 × 0.05 mm
V = 360.62 (8) Å³

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1917 independent reflections
Radiation source: fine-focus sealed tube	1913 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.078
φ and ω scans	θ_max = 29.2°, θ_min = 2.8°
Absorption correction: multi-scan (SADABS; Bruker, 2001)'	h = −4→5
T_min = 0.293, T_max = 0.523	k = −8→8
4417 measured reflections	l = −19→19

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 0.83	w = 1/[σ²(F_o²) + (0.0827P)²] where P = (F_o² + 2F_c²)/3
1917 reflections	(Δ/σ)_max = 0.015
98 parameters	Δρ_max = 1.02 e Å⁻³
0 restraints	Δρ_min = −1.22 e Å⁻³

Crystal data top

[HgCl₂(C₆H₅NO₂)₂]	γ = 92.963 (11)°
M_r = 517.71	V = 360.62 (8) Å³
Triclinic, P1	Z = 1
a = 3.8298 (5) Å	Mo Kα radiation
b = 6.5626 (9) Å	µ = 11.06 mm⁻¹
c = 14.5831 (18) Å	T = 298 K
α = 98.001 (10)°	0.20 × 0.10 × 0.05 mm
β = 95.315 (11)°

Data collection top

Bruker SMART 1000 CCD area-detector diffractometer	1917 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)'	1913 reflections with I > 2σ(I)
T_min = 0.293, T_max = 0.523	R_int = 0.078
4417 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 0.83	Δρ_max = 1.02 e Å⁻³
1917 reflections	Δρ_min = −1.22 e Å⁻³
98 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
C1	0.5737 (16)	0.5901 (8)	0.3289 (4)	0.0441 (10)
H1	0.6553	0.5307	0.3805	0.053*
C2	0.5746 (17)	0.4781 (8)	0.2408 (4)	0.0471 (11)
H2	0.6561	0.3463	0.2338	0.057*
C3	0.4531 (16)	0.5643 (8)	0.1635 (4)	0.0444 (10)
H3	0.4528	0.4926	0.1038	0.053*
C4	0.3308 (14)	0.7624 (7)	0.1775 (3)	0.0376 (8)
C5	0.1917 (15)	0.8656 (8)	0.0996 (3)	0.0419 (9)
C6	0.3410 (14)	0.8644 (7)	0.2680 (3)	0.0385 (8)
H6	0.2618	0.9966	0.2770	0.046*
N1	0.4590 (13)	0.7817 (7)	0.3425 (3)	0.0410 (8)
O1	0.0639 (17)	1.0378 (8)	0.1165 (3)	0.0595 (12)
O2	0.2082 (19)	0.7727 (9)	0.0170 (3)	0.0648 (14)
H2A	0.1115	0.8387	−0.0208	0.097*
Cl1	0.9257 (3)	0.77277 (19)	0.56211 (9)	0.0418 (2)
Hg1	0.5000	1.0000	0.5000	0.03700 (10)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.047 (3)	0.041 (2)	0.047 (2)	0.0095 (19)	−0.0002 (19)	0.0179 (18)
C2	0.055 (3)	0.035 (2)	0.053 (3)	0.0128 (19)	0.002 (2)	0.0103 (18)
C3	0.051 (3)	0.039 (2)	0.044 (2)	0.0099 (19)	0.0038 (19)	0.0065 (16)
C4	0.040 (2)	0.0376 (19)	0.0365 (19)	0.0052 (16)	0.0025 (15)	0.0083 (15)
C5	0.048 (3)	0.042 (2)	0.037 (2)	0.0091 (19)	−0.0016 (17)	0.0081 (16)
C6	0.046 (2)	0.0380 (19)	0.0340 (19)	0.0129 (17)	0.0010 (16)	0.0103 (15)
N1	0.047 (2)	0.0413 (19)	0.0361 (17)	0.0116 (17)	−0.0005 (15)	0.0119 (14)
O1	0.085 (4)	0.054 (2)	0.0421 (19)	0.032 (2)	0.000 (2)	0.0115 (16)
O2	0.098 (4)	0.064 (3)	0.0336 (18)	0.033 (3)	−0.001 (2)	0.0055 (16)
Cl1	0.0408 (5)	0.0432 (5)	0.0452 (5)	0.0145 (4)	0.0031 (4)	0.0164 (4)
Hg1	0.03475 (14)	0.04550 (15)	0.03275 (13)	0.01720 (9)	0.00034 (8)	0.00937 (8)

Geometric parameters (Å, º) top

C1—N1	1.348 (7)	C5—O1	1.257 (7)
C1—C2	1.390 (8)	C5—O2	1.281 (7)
C1—H1	0.9300	C6—N1	1.334 (6)
C2—C3	1.384 (8)	C6—H6	0.9300
C2—H2	0.9300	N1—Hg1	2.519 (4)
C3—C4	1.399 (7)	O2—H2A	0.8200
C3—H3	0.9300	Hg1—Cl1	2.4608 (13)
C4—C6	1.390 (6)	Hg1—Cl1ⁱ	2.8790 (13)
C4—C5	1.474 (7)	Hg1—N1ⁱⁱ	2.519 (4)

N1—C1—C2	122.4 (5)	C6—N1—Hg1	118.5 (3)
N1—C1—H1	118.8	C1—N1—Hg1	123.2 (3)
C2—C1—H1	118.8	C5—O2—H2A	109.5
C3—C2—C1	119.4 (5)	Hg1—Cl1—Hg1ⁱⁱⁱ	91.31 (4)
C3—C2—H2	120.3	Cl1—Hg1—Cl1ⁱⁱ	180.000 (1)
C1—C2—H2	120.3	Cl1—Hg1—N1ⁱⁱ	89.75 (11)
C2—C3—C4	118.2 (5)	Cl1ⁱⁱ—Hg1—N1ⁱⁱ	90.25 (11)
C2—C3—H3	120.9	Cl1—Hg1—N1	90.25 (11)
C4—C3—H3	120.9	Cl1ⁱⁱ—Hg1—N1	89.75 (11)
C3—C4—C6	118.7 (5)	N1ⁱⁱ—Hg1—N1	180.000 (1)
C3—C4—C5	122.1 (4)	Cl1—Hg1—Cl1ⁱ	91.31 (4)
C6—C4—C5	119.2 (5)	Cl1ⁱⁱ—Hg1—Cl1ⁱ	88.69 (4)
O1—C5—O2	123.2 (5)	N1ⁱⁱ—Hg1—Cl1ⁱ	85.85 (11)
O1—C5—C4	119.4 (5)	N1—Hg1—Cl1ⁱ	94.15 (11)
O2—C5—C4	117.4 (5)	Cl1—Hg1—Cl1^iv	88.69 (4)
N1—C6—C4	123.1 (5)	Cl1ⁱⁱ—Hg1—Cl1^iv	91.31 (4)
N1—C6—H6	118.4	N1ⁱⁱ—Hg1—Cl1^iv	94.15 (11)
C4—C6—H6	118.5	N1—Hg1—Cl1^iv	85.85 (11)
C6—N1—C1	118.1 (5)	Cl1ⁱ—Hg1—Cl1^iv	180.0

N1—C1—C2—C3	−0.2 (9)	Hg1ⁱⁱⁱ—Cl1—Hg1—N1ⁱⁱ	−94.16 (11)
C1—C2—C3—C4	−0.5 (9)	Hg1ⁱⁱⁱ—Cl1—Hg1—N1	85.84 (11)
C2—C3—C4—C6	0.8 (8)	Hg1ⁱⁱⁱ—Cl1—Hg1—Cl1ⁱ	180.0
C2—C3—C4—C5	−179.1 (5)	Hg1ⁱⁱⁱ—Cl1—Hg1—Cl1^iv	0.0
C3—C4—C5—O1	175.3 (6)	C6—N1—Hg1—Cl1	−159.3 (4)
C6—C4—C5—O1	−4.6 (8)	C1—N1—Hg1—Cl1	15.9 (4)
C3—C4—C5—O2	−4.6 (8)	C6—N1—Hg1—Cl1ⁱⁱ	20.7 (4)
C6—C4—C5—O2	175.4 (6)	C1—N1—Hg1—Cl1ⁱⁱ	−164.1 (4)
C3—C4—C6—N1	−0.7 (8)	C6—N1—Hg1—N1ⁱⁱ	−6 (100)
C5—C4—C6—N1	179.3 (5)	C1—N1—Hg1—N1ⁱⁱ	169 (100)
C4—C6—N1—C1	0.1 (8)	C6—N1—Hg1—Cl1ⁱ	109.4 (4)
C4—C6—N1—Hg1	175.5 (4)	C1—N1—Hg1—Cl1ⁱ	−75.4 (4)
C2—C1—N1—C6	0.4 (8)	C6—N1—Hg1—Cl1^iv	−70.6 (4)
C2—C1—N1—Hg1	−174.8 (4)	C1—N1—Hg1—Cl1^iv	104.6 (4)
Hg1ⁱⁱⁱ—Cl1—Hg1—Cl1ⁱⁱ	73 (100)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1^v	0.82	1.80	2.618 (7)	171
C1—H1···Cl1^vi	0.93	2.79	3.582 (6)	144
C6—H6···Cl1ⁱⁱ	0.93	2.78	3.454 (5)	130

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

Experimental details

Crystal data
Chemical formula	[HgCl₂(C₆H₅NO₂)₂]
M_r	517.71
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	3.8298 (5), 6.5626 (9), 14.5831 (18)
α, β, γ (°)	98.001 (10), 95.315 (11), 92.963 (11)
V (Å³)	360.62 (8)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	11.06
Crystal size (mm)	0.20 × 0.10 × 0.05

Data collection
Diffractometer	Bruker SMART 1000 CCD area-detector
Absorption correction	Multi-scan (SADABS; Bruker, 2001)'
T_min, T_max	0.293, 0.523
No. of measured, independent and observed [I > 2σ(I)] reflections	4417, 1917, 1913
R_int	0.078
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.082, 0.83
No. of reflections	1917
No. of parameters	98
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.02, −1.22

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Selected bond lengths (Å) top

Hg1—Cl1	2.4608 (13)	Hg1—N1ⁱⁱ	2.519 (4)
Hg1—Cl1ⁱ	2.8790 (13)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2A···O1ⁱⁱⁱ	0.82	1.80	2.618 (7)	171
C1—H1···Cl1^iv	0.93	2.79	3.582 (6)	144
C6—H6···Cl1ⁱⁱ	0.93	2.78	3.454 (5)	130

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

Acknowledgements

We are grateful to the Islamic Azad University, Omidieh Branch for financial support.

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