Di-μ-chlorido-bis­[(2-amino-4-methyl­pyridine-κN)­chloridomercury(II)]

Tadjarodi, A.; Bijanzad, K.; Notash, B.

doi:10.1107/S1600536812039803

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 10| October 2012| Pages m1300-m1301

https://doi.org/10.1107/S1600536812039803

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Di-μ-chlorido-bis[(2-amino-4-methylpyridine-κN)chloridomercury(II)]

Azadeh Tadjarodi,^a ^* Keyvan Bijanzad ^a and Behrouz Notash ^b

^aDepartment of Chemistry, Iran University of Science and Technology, Tehran 16846-13114, Iran, and ^bDepartment of Chemistry, Shahid Beheshti University, G. C., Evin, Tehran 1983963113, Iran
^*Correspondence e-mail: tajarodi@iust.ac.ir

(Received 20 August 2012; accepted 19 September 2012; online 26 September 2012)

In the centrosymmetric dinuclear title compound, [Hg₂Cl₄(C₆H₈N₂)₂], the Hg^II ion is four-coordinated by one pyridine N atom from a 2-amino-4-methylpyridine ligand, one terminal Cl atom and two bridging Cl atoms. A distorted tetrahedral geometry is formed around each Hg^II ion. The crystal packing is stabilized by intra- and intermolecular N—H⋯Cl hydrogen bonding. There are also π–π stacking interactions in the structure, with centroid-to-centroid distances of 3.594 (6) Å.

Related literature

For a coordination compound of 2-amino-4-methylpyridine, see: Arab Ahmadi et al. (2011 ). For proton-transfer compounds of 2-amino-4-methylpyridine, see: Gharbia et al. (2008 ); Choudhury et al. (2009 ); Das et al. (2010 ); Hemamalini & Fun (2010 ); Aghabozorg et al. (2011 ); Eshtiagh-Hosseini et al. (2010 ). For mixed-ligand complexes of 2-amino-4-methylpyridine, see: Zhang et al. (2008 ); Castillo et al. (2001 ); Yenikaya et al. (2011 ). For similar structures, see: Baul et al. (2004 ).

Experimental

Crystal data

[Hg₂Cl₄(C₆H₈N₂)₂]
M_r = 759.27
Monoclinic, P 2/n
a = 7.1777 (14) Å
b = 9.1672 (18) Å
c = 14.546 (3) Å
β = 101.92 (3)°
V = 936.5 (3) Å³
Z = 2
Mo Kα radiation
μ = 16.94 mm⁻¹
T = 120 K
0.25 × 0.25 × 0.20 mm

Data collection

Stoe IPDS 2T diffractometer
Absorption correction: numerical (shape of crystal determined optically; X-RED and X-SHAPE, Stoe & Cie, 2005 ) T_min = 0.101, T_max = 0.133
6495 measured reflections
2507 independent reflections
2019 reflections with I > 2σ(I)
R_int = 0.090

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.111
S = 1.00
2507 reflections
109 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 2.35 e Å⁻³
Δρ_min = −2.80 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯Cl2ⁱ	0.87 (2)	2.62 (7)	3.380 (8)	146 (11)
N2—H2A⋯Cl2ⁱⁱ	0.87 (2)	2.68 (11)	3.379 (9)	139 (13)
Symmetry codes: (i) -x, -y+1, -z+2; (ii) $[x-{\script{1\over 2}}, -y+1, z-{\script{1\over 2}}]$ .

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA; data reduction: X-AREA; 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: https://doi.org/10.1107/S1600536812039803/bt6826sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812039803/bt6826Isup2.hkl

checkCIF report

Comment top

To the best of our knowledge, coordination chemistry of 2-amino-4-methylpyridine has not been explored sufficiently. It has the potential to coordinate to metals through the N atom of the pyridyl group (Arab Ahmadi et al., 2011).

Contrary to other derivatives of aminopicolines, less work has been done on the synthesis of the complexes merely containing 2-amino-4-methylpyridine and most of the work is focused on its mixed ligand complexes (Zhang et al., 2008; Castillo et al., 2001; Yenikaya et al., 2011) or proton transfer compounds (Gharbia et al., 2008; Choudhury et al., 2009; Das et al., 2010; Hemamalini & Fun, 2010; Aghabozorg et al., 2011; Eshtiagh-Hosseini et al., 2010).

Herein, we report the synthesis and crystal structure of the title compound, [Hg₂(C₆H₈N₂)₂Cl₄], which is a dimeric complex. The centrosymmetric structure is made up of two Hg atoms, each coordinated by a terminal chloride atom and a nitrogen pyridyl ligand and bridged by chloride atoms. A distorted tetrahedral geometry is formed around each metal center (Fig. 1). The asymmetric unit contains one-half of a molecule since the whole molecule lies across a crystallographic inversion center. Bridging chloride atoms along with amino groups take part in intra- and intermolecular N—H··· Cl hydrogen bonds (Fig. 2 and Table 1). There is also π–π stacking in the structure of title compound with centroid–centroid distance of 3.594 (6) Å (Fig. 2).

Related literature top

For a coordination compound of 2-amino-4-methylpyridine, see: Arab Ahmadi et al. (2011). For proton-transfer compounds of 2-amino-4-methylpyridine, see: Gharbia et al. (2008); Choudhury et al. (2009); Das et al. (2010); Hemamalini & Fun (2010); Aghabozorg et al. (2011); Eshtiagh-Hosseini et al. (2010). For mixed-ligand complexes of 2-amino-4-methylpyridine, see: Zhang et al. (2008); Castillo et al. (2001); Yenikaya et al. (2011). For similar structures, see: Baul et al. (2004).

Experimental top

A solution of 2-amino-4-methylpyridine (1 mmol) in methanol was added to a methanolic solution of HgCl₂ (1 mmol) and stirred for 20 min at 50°C. Slow evaporation of the resulting solution gave colorless crystals suitable for X-ray analysis.

Structure description top

For a coordination compound of 2-amino-4-methylpyridine, see: Arab Ahmadi et al. (2011). For proton-transfer compounds of 2-amino-4-methylpyridine, see: Gharbia et al. (2008); Choudhury et al. (2009); Das et al. (2010); Hemamalini & Fun (2010); Aghabozorg et al. (2011); Eshtiagh-Hosseini et al. (2010). For mixed-ligand complexes of 2-amino-4-methylpyridine, see: Zhang et al. (2008); Castillo et al. (2001); Yenikaya et al. (2011). For similar structures, see: Baul et al. (2004).

Computing details top

Data collection: X-AREA (Stoe & Cie, 2005); cell refinement: X-AREA (Stoe & Cie, 2005); data reduction: X-AREA (Stoe & Cie, 2005); 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 [Hg₂(C₆H₈N₂)₂Cl₄] with displacement ellipsoids drawn at 30% probability level.
	Fig. 2. The packing diagram of the title compound showing hydrogen bonding as blue dashed lines and π–π stacking.

Di-µ-chlorido-bis[(2-amino-4-methylpyridine)chloridomercury(II)] top

Crystal data top

C₁₂H₁₆Cl₄Hg₂N₄	F(000) = 688
M_r = 759.27	D_x = 2.693 Mg m⁻³
Monoclinic, P2/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yac	Cell parameters from 2507 reflections
a = 7.1777 (14) Å	θ = 2.6–29.1°
b = 9.1672 (18) Å	µ = 16.94 mm⁻¹
c = 14.546 (3) Å	T = 120 K
β = 101.92 (3)°	Block, colorless
V = 936.5 (3) Å³	0.25 × 0.25 × 0.20 mm
Z = 2

Data collection top

Stoe IPDS 2T diffractometer	2507 independent reflections
Radiation source: fine-focus sealed tube	2019 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.090
Detector resolution: 0.15 mm pixels mm^-1	θ_max = 29.1°, θ_min = 2.6°
rotation method scans	h = −9→9
Absorption correction: numerical shape of crystal determined optically	k = −12→10
T_min = 0.101, T_max = 0.133	l = −19→19
6495 measured reflections

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ²(F_o²) + (0.0604P)²] where P = (F_o² + 2F_c²)/3
2507 reflections	(Δ/σ)_max < 0.001
109 parameters	Δρ_max = 2.35 e Å⁻³
2 restraints	Δρ_min = −2.80 e Å⁻³

Crystal data top

C₁₂H₁₆Cl₄Hg₂N₄	V = 936.5 (3) Å³
M_r = 759.27	Z = 2
Monoclinic, P2/n	Mo Kα radiation
a = 7.1777 (14) Å	µ = 16.94 mm⁻¹
b = 9.1672 (18) Å	T = 120 K
c = 14.546 (3) Å	0.25 × 0.25 × 0.20 mm
β = 101.92 (3)°

Data collection top

Stoe IPDS 2T diffractometer	2507 independent reflections
Absorption correction: numerical shape of crystal determined optically	2019 reflections with I > 2σ(I)
T_min = 0.101, T_max = 0.133	R_int = 0.090
6495 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	2 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	Δρ_max = 2.35 e Å⁻³
2507 reflections	Δρ_min = −2.80 e Å⁻³
109 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	0.21238 (5)	0.47797 (4)	0.94011 (2)	0.02164 (12)
Cl1	0.3952 (3)	0.6882 (3)	0.98493 (15)	0.0237 (4)
Cl2	0.1382 (3)	0.3856 (2)	1.10331 (13)	0.0205 (4)
N1	0.1135 (11)	0.2841 (9)	0.8633 (5)	0.0210 (15)
N2	0.0000 (13)	0.4145 (10)	0.7272 (5)	0.0278 (18)
C1	0.0312 (12)	0.2842 (11)	0.7714 (6)	0.0221 (18)
C2	−0.0152 (13)	0.1524 (12)	0.7224 (6)	0.025 (2)
H2	−0.0709	0.1541	0.6572	0.030*
C3	0.0199 (16)	0.0208 (12)	0.7685 (7)	0.031 (2)
C4	−0.022 (2)	−0.1198 (14)	0.7162 (8)	0.046 (3)
H4A	−0.1242	−0.1048	0.6610	0.068*
H4B	−0.0612	−0.1931	0.7573	0.068*
H4C	0.0930	−0.1536	0.6959	0.068*
C5	0.0993 (15)	0.0221 (12)	0.8661 (7)	0.028 (2)
H5	0.1206	−0.0662	0.9009	0.034*
C6	0.1444 (14)	0.1542 (11)	0.9089 (6)	0.0241 (18)
H6	0.2003	0.1550	0.9741	0.029*
H2A	−0.080 (14)	0.429 (19)	0.675 (5)	0.06 (4)*
H2B	−0.028 (19)	0.495 (7)	0.753 (9)	0.03 (3)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Hg1	0.02222 (18)	0.0215 (2)	0.01994 (17)	−0.00052 (14)	0.00134 (11)	−0.00125 (13)
Cl1	0.0237 (10)	0.0218 (12)	0.0245 (10)	−0.0020 (8)	0.0025 (8)	0.0015 (8)
Cl2	0.0194 (9)	0.0248 (11)	0.0177 (8)	0.0030 (8)	0.0047 (7)	0.0008 (7)
N1	0.021 (4)	0.020 (4)	0.022 (3)	−0.003 (3)	0.005 (3)	−0.001 (3)
N2	0.040 (5)	0.026 (5)	0.016 (3)	0.010 (4)	0.001 (3)	−0.001 (3)
C1	0.010 (4)	0.033 (5)	0.024 (4)	0.001 (3)	0.005 (3)	0.003 (3)
C2	0.020 (4)	0.038 (6)	0.017 (4)	−0.004 (4)	0.006 (3)	−0.010 (4)
C3	0.038 (6)	0.033 (6)	0.026 (4)	−0.015 (4)	0.017 (4)	−0.012 (4)
C4	0.073 (9)	0.036 (7)	0.033 (5)	−0.030 (6)	0.023 (6)	−0.022 (5)
C5	0.033 (5)	0.023 (5)	0.031 (5)	0.003 (4)	0.014 (4)	0.002 (4)
C6	0.025 (5)	0.026 (5)	0.019 (4)	0.001 (4)	0.002 (3)	0.002 (3)

Geometric parameters (Å, º) top

Hg1—N1	2.141 (8)	C2—C3	1.377 (16)
Hg1—Cl1	2.347 (2)	C2—H2	0.9500
Hg1—Cl2	2.6755 (19)	C3—C5	1.417 (16)
Hg1—Cl2ⁱ	2.763 (2)	C3—C4	1.496 (14)
Cl2—Hg1ⁱ	2.763 (2)	C4—H4A	0.9800
N1—C1	1.345 (12)	C4—H4B	0.9800
N1—C6	1.359 (13)	C4—H4C	0.9800
N2—C1	1.353 (13)	C5—C6	1.369 (15)
N2—H2A	0.87 (2)	C5—H5	0.9500
N2—H2B	0.87 (2)	C6—H6	0.9500
C1—C2	1.407 (14)

N1—Hg1—Cl1	158.87 (19)	C3—C2—H2	119.8
N1—Hg1—Cl2	95.45 (19)	C1—C2—H2	119.8
Cl1—Hg1—Cl2	102.46 (7)	C2—C3—C5	118.4 (9)
N1—Hg1—Cl2ⁱ	93.9 (2)	C2—C3—C4	120.6 (10)
Cl1—Hg1—Cl2ⁱ	97.04 (8)	C5—C3—C4	120.9 (11)
Cl2—Hg1—Cl2ⁱ	90.41 (7)	C3—C4—H4A	109.5
Hg1—Cl2—Hg1ⁱ	89.59 (7)	C3—C4—H4B	109.5
C1—N1—C6	118.7 (9)	H4A—C4—H4B	109.5
C1—N1—Hg1	123.2 (7)	C3—C4—H4C	109.5
C6—N1—Hg1	118.0 (6)	H4A—C4—H4C	109.5
C1—N2—H2A	125 (10)	H4B—C4—H4C	109.5
C1—N2—H2B	125 (9)	C6—C5—C3	118.1 (10)
H2A—N2—H2B	94 (10)	C6—C5—H5	121.0
N1—C1—N2	117.9 (9)	C3—C5—H5	121.0
N1—C1—C2	120.8 (9)	N1—C6—C5	123.6 (9)
N2—C1—C2	121.3 (8)	N1—C6—H6	118.2
C3—C2—C1	120.3 (8)	C5—C6—H6	118.2

N1—Hg1—Cl2—Hg1ⁱ	−94.0 (2)	C6—N1—C1—C2	−2.5 (12)
Cl1—Hg1—Cl2—Hg1ⁱ	97.30 (8)	Hg1—N1—C1—C2	174.1 (6)
Cl2ⁱ—Hg1—Cl2—Hg1ⁱ	0.0	N1—C1—C2—C3	1.2 (12)
Cl1—Hg1—N1—C1	−64.4 (10)	N2—C1—C2—C3	179.2 (9)
Cl2—Hg1—N1—C1	147.6 (6)	C1—C2—C3—C5	1.4 (14)
Cl2ⁱ—Hg1—N1—C1	56.8 (6)	C1—C2—C3—C4	−177.6 (9)
Cl1—Hg1—N1—C6	112.2 (7)	C2—C3—C5—C6	−2.6 (15)
Cl2—Hg1—N1—C6	−35.8 (6)	C4—C3—C5—C6	176.3 (9)
Cl2ⁱ—Hg1—N1—C6	−126.6 (6)	C1—N1—C6—C5	1.2 (13)
C6—N1—C1—N2	179.4 (8)	Hg1—N1—C6—C5	−175.6 (7)
Hg1—N1—C1—N2	−4.0 (11)	C3—C5—C6—N1	1.4 (15)

Symmetry code: (i) −x, −y+1, −z+2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···Cl2ⁱ	0.87 (2)	2.62 (7)	3.380 (8)	146 (11)
N2—H2A···Cl2ⁱⁱ	0.87 (2)	2.68 (11)	3.379 (9)	139 (13)

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

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆Cl₄Hg₂N₄
M_r	759.27
Crystal system, space group	Monoclinic, P2/n
Temperature (K)	120
a, b, c (Å)	7.1777 (14), 9.1672 (18), 14.546 (3)
β (°)	101.92 (3)
V (Å³)	936.5 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	16.94
Crystal size (mm)	0.25 × 0.25 × 0.20

Data collection
Diffractometer	Stoe IPDS 2T
Absorption correction	Numerical shape of crystal determined optically
T_min, T_max	0.101, 0.133
No. of measured, independent and observed [I > 2σ(I)] reflections	6495, 2507, 2019
R_int	0.090
(sin θ/λ)_max (Å⁻¹)	0.685

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.111, 1.00
No. of reflections	2507
No. of parameters	109
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	2.35, −2.80

Computer programs: X-AREA (Stoe & Cie, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···Cl2ⁱ	0.87 (2)	2.62 (7)	3.380 (8)	146 (11)
N2—H2A···Cl2ⁱⁱ	0.87 (2)	2.68 (11)	3.379 (9)	139 (13)

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

Acknowledgements

The authors acknowledge the Iran University of Science and Technology (IUST) for financial support.

References

Aghabozorg, H., Mofidi Rouchi, A., Mirzaei, M. & Notash, B. (2011). Acta Cryst. E67, o54. Web of Science CrossRef IUCr Journals Google Scholar
Arab Ahmadi, R., Safari, N., Khavasi, H. R. & Amani, S. (2011). J. Coord. Chem. 64, 2056–2065. Google Scholar
Baul, T. S. B., Lycka, A., Butcher, R. & Smith, E. F. (2004). Polyhedron, 23, 2323–2329. Google Scholar
Castillo, O., Luque, A., Julve, M., Lloret, F. & Roman, P. (2001). Inorg. Chim. Acta, 315, 9–17. Web of Science CSD CrossRef CAS Google Scholar
Choudhury, S. R., Dey, B., Das, S., Robertazzi, A., Jana, A. D., Chen, C. Y., Lee, H. M., Gameze, P. & Mukhopadhyay, S. (2009). Dalton Trans. pp. 7617–7624. Web of Science CSD CrossRef Google Scholar
Das, A., Choudhury, S. R., Dey, B., Yalamanchili, S. K., Helliwell, M., Gamez, P., Mukhopadhyay, S., Estarellas, C. & Frontera, A. (2010). J. Phys. Chem. B, 114, 4998–5009. Web of Science CSD CrossRef CAS PubMed Google Scholar
Eshtiagh-Hosseini, H., Aghabozorg, H., Mirzaei, M., Amini, M. M., Chen, Y. G., Shokrollahi, A. & Aghaei, R. (2010). J. Mol. Struct. 973, 180–189. CAS Google Scholar
Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565. CrossRef IUCr Journals Google Scholar
Farrugia, L. J. (1999). J. Appl. Cryst. 32, 837–838. CrossRef CAS IUCr Journals Google Scholar
Gharbia, I. B., Kefi, R., Nasr, C. B. & Durif, A. (2008). Rev. Roum. Chim. 53, 169–175. Google Scholar
Hemamalini, M. & Fun, H.-K. (2010). Acta Cryst. E66, o2151–o2152. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Stoe & Cie (2005). X-AREA, X-RED and X-SHAPE. Stoe & Cie, Darmstadt, Germany. Google Scholar
Yenikaya, C., Büyükkidany, N., Sariz, M., Keşli, R., Ilkimeny, H., Bülbüly, M. & Büyükgüngor, O. (2011). J. Coord. Chem. 64, 3353–3365. Web of Science CSD CrossRef CAS Google Scholar
Zhang, L., You, Z. & Jiao, Q. (2008). Transition Met. Chem. 33, 573–577. Web of Science CSD CrossRef CAS Google Scholar