catena-Poly[di-μ3-bromido-hexa-μ2-bromido-dibromidobis(O-methyl pyridine-2-carboximidate-κ2N,N′)penta­mercury(II)]

Shirvan, S.A.; Hossaini Sadr, M.

doi:10.1107/S1600536812046545

metal-organic compounds

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Volume 68| Part 12| December 2012| Page m1492

doi:10.1107/S1600536812046545

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catena-Poly[di-μ₃-bromido-hexa-μ₂-bromido-dibromidobis(O-methyl pyridine-2-carboximidate-κ²N,N′)pentamercury(II)]

Sadif A. Shirvan ^a ^* and Moayad Hossaini Sadr ^b

^aDepartment of Chemistry, Omidieh Branch, Islamic Azad University, Omidieh, Iran, and ^bDepartment of Chemistry, Faculty of Science, Azarbaijan Shahid Madani University, Tabriz, Iran
^*Correspondence e-mail: sadifchemist@hotmail.com

(Received 3 November 2012; accepted 11 November 2012; online 17 November 2012)

The title compound, [Hg₅Br₁₀(C₇H₈N₂O)₂]_n, contains two μ₃-bridging Br atoms, six μ₂-bridging Br atoms and two terminal Br atoms. One Hg^II atom, lying on an inversion center, adopts a distorted octahedral geometry defined by six Br atoms. Two Hg^II atoms adopt a distorted square-pyramidal geometry by five Br atoms and the other two Hg^II atoms have a distorted tetrahedral geometry by two N atoms from a chelating O-methyl pyridine-2-carboximidate ligand and two Br atoms. The Br atoms link the Hg^II atoms into a ribbon structure along [100].

Related literature

For metal complexes with O-alkyl pyridine-2-carboximidate, see: Barnard (1969 ); Du et al. (2005 , 2006 ); Jamnicky et al. (1995 ); Seglá & Jamnicky (1988 ); Suzuki et al. (1974 ).

Experimental

Crystal data

[Hg₅Br₁₀(C₇H₈N₂O)₂]
M_r = 2074.26
Triclinic, $[P \overline 1]$
a = 7.6768 (7) Å
b = 10.7223 (10) Å
c = 11.0663 (10) Å
α = 92.067 (7)°
β = 102.850 (7)°
γ = 101.879 (7)°
V = 865.86 (14) Å³
Z = 1
Mo Kα radiation
μ = 33.65 mm⁻¹
T = 298 K
0.30 × 0.19 × 0.18 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.105, T_max = 0.223
7320 measured reflections
3410 independent reflections
2042 reflections with I > 2σ(I)
R_int = 0.084

Refinement

R[F² > 2σ(F²)] = 0.062
wR(F²) = 0.148
S = 0.93
3410 reflections
160 parameters
H-atom parameters constrained
Δρ_max = 1.89 e Å⁻³
Δρ_min = −1.90 e Å⁻³

Table 1
Selected bond lengths (Å)

Hg1—N1	2.322 (14)
Hg1—N2	2.400 (16)
Hg1—Br1	2.524 (2)
Hg1—Br2	2.534 (2)
Hg2—Br2	3.204 (2)
Hg2—Br3	2.438 (2)
Hg2—Br5	3.189 (2)
Hg3—Br1	3.119 (2)
Hg3—Br2ⁱ	3.140 (2)
Hg3—Br3	3.337 (2)
Hg3—Br4	2.418 (2)
Hg3—Br5	2.463 (2)
Symmetry code: (i) x+1, y, z.

Data collection: APEX2 (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 (Farrugia, 2012 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812046545/hy2602sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812046545/hy2602Isup2.hkl

checkCIF report

Comment top

As has previously been observed, the reaction of 2-cyanopyridine (2-cnpy) with water or an alcohol in the presence of some metal(II) salts leads to the formation of complexes which contain O-alkylpyridine-2-carboximidate (Barnard, 1969; Seglá & Jamnicky, 1988; Suzuki et al., 1974). The reaction of 2-cnpy and Cu^II (Du et al., 2005), Cd^II (Du et al., 2006) and Ni^II (Jamnicky et al., 1995) in methanol leads to the formation of a chelate ligand, O-methylpyridine-2-carboximidate. Here, we report the synthesis and structure of the title compound.

The asymmetric unit of the title compound (Fig. 1) consists of 2.5 crystallographically independent Hg^II atoms, five bromide ions and one neutral O-methylpyridine-2-carboximidate ligand. The Br2 atom adopts a µ₃-mode to bridge three Hg^II atoms, while Br1, Br3 and Br5 are coordinated to Hg^II atoms in a µ₂-mode. The Br4 atom is coordinated to one Hg^II atom in a terminal fashion. The Hg1 atom adopts a distorted tetrahedral coordination geometry defined by two N atoms from one O-methylpyridine-2-carboximidate ligand and two Br atoms. The Hg2 atom, lying on an inversion center, adopts a distorted octahedral geometry by six Br atoms and Hg3 atom adopts a distorted square-pyramidal geometry by five Br atoms (Table 1). The Hg^II atoms are linked by the Br atoms into a ribbon structure along [100].

Related literature top

For metal complexes with O-alkyl pyridine-2-carboximidate, see: Barnard (1969); Du et al. (2005, 2006); Jamnicky et al. (1995); Seglá & Jamnicky (1988); Suzuki et al. (1974).

Experimental top

For the preparation of the title compound, a solution of 2-cyanopyridine (0.47 g, 4.42 mmol) in methanol (10 ml) was added to a solution of HgBr₂ (0.82 g, 2.21 mmol) in methanol (10 ml) and the resulting yellow solution was stirred for 20 min at room temperature. This solution was left to evaporate slowly at room temperature. After one week, yellow prismatic crystals of the title compound were isolated (yield: 0.75 g, 83.4%).

Computing details top

Data collection: APEX2 (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 (Farrugia, 2012); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The asymmetric unit of the title compound. Displacement ellipsoids are drawn at the 50% probability level. [Symmetry codes: (a) -1+x, y, z; (b) 1+x, y, z; (c) 1-x, 1-y, -z.]
	Fig. 2. Crystal packing diagram for the title compound.

catena-Poly[di-µ₃-bromido-hexa-µ₂-bromido- dibromidobis(O-methyl pyridine-2-carboximidate-κ²N,N')pentamercury(II)] top

Crystal data top

[Hg₅Br₁₀(C₇H₈N₂O)₂]	Z = 1
M_r = 2074.26	F(000) = 894
Triclinic, P1	D_x = 3.978 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.6768 (7) Å	Cell parameters from 7320 reflections
b = 10.7223 (10) Å	θ = 1.9–26.0°
c = 11.0663 (10) Å	µ = 33.65 mm⁻¹
α = 92.067 (7)°	T = 298 K
β = 102.850 (7)°	Prism, yellow
γ = 101.879 (7)°	0.30 × 0.19 × 0.18 mm
V = 865.86 (14) Å³

Data collection top

Bruker APEXII CCD diffractometer	3410 independent reflections
Radiation source: fine-focus sealed tube	2042 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.084
ϕ and ω scans	θ_max = 26.0°, θ_min = 1.9°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −9→9
T_min = 0.105, T_max = 0.223	k = −13→13
7320 measured reflections	l = −13→13

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)] = 0.062	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.148	H-atom parameters constrained
S = 0.93	w = 1/[σ²(F_o²) + (0.0731P)²] where P = (F_o² + 2F_c²)/3
3410 reflections	(Δ/σ)_max = 0.003
160 parameters	Δρ_max = 1.89 e Å⁻³
0 restraints	Δρ_min = −1.90 e Å⁻³

Crystal data top

[Hg₅Br₁₀(C₇H₈N₂O)₂]	γ = 101.879 (7)°
M_r = 2074.26	V = 865.86 (14) Å³
Triclinic, P1	Z = 1
a = 7.6768 (7) Å	Mo Kα radiation
b = 10.7223 (10) Å	µ = 33.65 mm⁻¹
c = 11.0663 (10) Å	T = 298 K
α = 92.067 (7)°	0.30 × 0.19 × 0.18 mm
β = 102.850 (7)°

Data collection top

Bruker APEXII CCD diffractometer	3410 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	2042 reflections with I > 2σ(I)
T_min = 0.105, T_max = 0.223	R_int = 0.084
7320 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.062	0 restraints
wR(F²) = 0.148	H-atom parameters constrained
S = 0.93	Δρ_max = 1.89 e Å⁻³
3410 reflections	Δρ_min = −1.90 e Å⁻³
160 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	−0.003 (4)	0.838 (2)	−0.726 (2)	0.076 (7)
H1A	−0.0886	0.7662	−0.7095	0.091*
H1B	0.0734	0.8091	−0.7743	0.091*
H1C	−0.0680	0.8955	−0.7723	0.091*
C2	0.211 (2)	0.8446 (18)	−0.5315 (18)	0.046 (4)
C3	0.327 (3)	0.9261 (17)	−0.4289 (17)	0.046 (4)
C4	0.329 (3)	1.0579 (19)	−0.4102 (19)	0.056 (5)
H4	0.2567	1.0962	−0.4702	0.067*
C5	0.434 (3)	1.128 (2)	−0.3060 (19)	0.057 (5)
H5	0.4316	1.2142	−0.2930	0.069*
C6	0.540 (3)	1.075 (2)	−0.223 (2)	0.063 (6)
H6	0.6140	1.1230	−0.1517	0.076*
C7	0.539 (3)	0.948 (2)	−0.244 (2)	0.065 (6)
H7	0.6186	0.9131	−0.1855	0.078*
N1	0.211 (2)	0.7237 (14)	−0.5445 (16)	0.054 (4)
H1D	0.1406	0.6742	−0.6067	0.065*
N2	0.435 (3)	0.8714 (16)	−0.3409 (15)	0.059 (5)
O1	0.110 (2)	0.9040 (13)	−0.6109 (12)	0.062 (4)
Hg1	0.41370 (13)	0.64830 (8)	−0.39109 (9)	0.0623 (3)
Hg2	0.5000	0.5000	0.0000	0.0588 (3)
Hg3	0.95464 (12)	0.64042 (7)	−0.14661 (8)	0.0591 (3)
Br1	0.7283 (3)	0.6379 (2)	−0.4186 (2)	0.0619 (6)
Br2	0.2253 (3)	0.5162 (2)	−0.26046 (19)	0.0549 (5)
Br3	0.6541 (3)	0.72282 (19)	−0.0001 (2)	0.0607 (5)
Br4	1.1178 (4)	0.8617 (2)	−0.1174 (3)	0.0788 (7)
Br5	0.7893 (3)	0.41969 (18)	−0.1371 (2)	0.0544 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.070 (15)	0.080 (16)	0.076 (17)	0.026 (13)	0.004 (13)	0.002 (13)
C2	0.027 (9)	0.057 (11)	0.051 (12)	0.002 (8)	0.008 (8)	0.012 (9)
C3	0.049 (10)	0.043 (9)	0.038 (10)	−0.010 (8)	0.011 (9)	0.005 (8)
C4	0.057 (12)	0.055 (12)	0.051 (13)	0.007 (10)	0.007 (10)	−0.001 (10)
C5	0.061 (13)	0.053 (11)	0.052 (12)	0.001 (10)	0.016 (11)	−0.018 (9)
C6	0.058 (13)	0.058 (13)	0.072 (15)	−0.002 (11)	0.028 (12)	−0.011 (11)
C7	0.053 (13)	0.065 (14)	0.058 (14)	−0.023 (11)	0.006 (11)	0.007 (11)
N1	0.059 (10)	0.035 (8)	0.068 (11)	0.019 (8)	0.008 (9)	0.007 (7)
N2	0.078 (12)	0.051 (9)	0.038 (9)	0.015 (9)	−0.008 (9)	0.003 (7)
O1	0.078 (10)	0.055 (8)	0.047 (8)	0.030 (8)	−0.010 (7)	−0.003 (6)
Hg1	0.0624 (5)	0.0600 (5)	0.0714 (6)	0.0192 (4)	0.0229 (4)	0.0187 (4)
Hg2	0.0572 (7)	0.0560 (6)	0.0657 (8)	0.0076 (5)	0.0246 (6)	0.0032 (5)
Hg3	0.0575 (5)	0.0477 (4)	0.0686 (6)	0.0021 (4)	0.0159 (4)	0.0045 (4)
Br1	0.0548 (12)	0.0756 (14)	0.0564 (13)	0.0195 (11)	0.0106 (10)	0.0052 (10)
Br2	0.0528 (11)	0.0612 (12)	0.0505 (12)	0.0070 (9)	0.0162 (9)	0.0068 (9)
Br3	0.0698 (14)	0.0512 (11)	0.0631 (13)	0.0113 (10)	0.0208 (11)	0.0071 (9)
Br4	0.0762 (16)	0.0521 (12)	0.0983 (19)	−0.0031 (11)	0.0148 (14)	0.0127 (12)
Br5	0.0573 (12)	0.0446 (10)	0.0632 (13)	0.0040 (9)	0.0263 (10)	−0.0037 (9)

Geometric parameters (Å, º) top

C1—O1	1.44 (3)	C7—N2	1.32 (3)
C1—H1A	0.9600	C7—H7	0.9300
C1—H1B	0.9600	Hg1—N1	2.322 (14)
C1—H1C	0.9600	N1—H1D	0.8600
C2—N1	1.30 (2)	Hg1—N2	2.400 (16)
C2—O1	1.313 (19)	Hg1—Br1	2.524 (2)
C2—C3	1.42 (3)	Hg1—Br2	2.534 (2)
C3—N2	1.36 (2)	Hg2—Br2	3.204 (2)
C3—C4	1.42 (3)	Hg2—Br3	2.438 (2)
C4—C5	1.35 (3)	Hg2—Br5	3.189 (2)
C4—H4	0.9300	Hg3—Br1	3.119 (2)
C5—C6	1.31 (3)	Hg3—Br2ⁱ	3.140 (2)
C5—H5	0.9300	Hg3—Br3	3.337 (2)
C6—C7	1.38 (3)	Hg3—Br4	2.418 (2)
C6—H6	0.9300	Hg3—Br5	2.463 (2)

O1—C1—H1A	109.5	N2—C7—C6	125 (2)
O1—C1—H1B	109.5	N2—C7—H7	117.5
H1A—C1—H1B	109.5	C6—C7—H7	117.5
O1—C1—H1C	109.5	C2—N1—Hg1	116.5 (13)
H1A—C1—H1C	109.5	C2—N1—H1D	121.7
H1B—C1—H1C	109.5	Hg1—N1—H1D	121.7
N1—C2—O1	124.8 (18)	C7—N2—C3	116.5 (17)
N1—C2—C3	121.8 (16)	C7—N2—Hg1	129.5 (14)
O1—C2—C3	113.4 (17)	C3—N2—Hg1	113.9 (12)
N2—C3—C2	117.1 (16)	C2—O1—C1	120.6 (16)
N2—C3—C4	119.2 (17)	N1—Hg1—N2	70.5 (5)
C2—C3—C4	123.6 (17)	N1—Hg1—Br1	120.2 (4)
C5—C4—C3	120.6 (18)	N2—Hg1—Br1	104.2 (5)
C5—C4—H4	119.7	N1—Hg1—Br2	107.2 (4)
C3—C4—H4	119.7	N2—Hg1—Br2	109.5 (5)
C6—C5—C4	120 (2)	Br1—Hg1—Br2	128.56 (7)
C6—C5—H5	120.2	Br3ⁱⁱ—Hg2—Br3	180.0
C4—C5—H5	120.2	Br4—Hg3—Br5	169.89 (9)
C5—C6—C7	119 (2)	Br4—Hg3—Br1	98.67 (8)
C5—C6—H6	120.5	Br5—Hg3—Br1	89.75 (7)
C7—C6—H6	120.5	Hg1—Br1—Hg3	103.35 (8)

N1—C2—C3—N2	−3 (3)	N1—C2—O1—C1	−4 (3)
O1—C2—C3—N2	179.0 (17)	C3—C2—O1—C1	173.9 (19)
N1—C2—C3—C4	−179.0 (19)	C2—N1—Hg1—N2	1.7 (14)
O1—C2—C3—C4	3 (3)	C2—N1—Hg1—Br1	−93.8 (14)
N2—C3—C4—C5	−1 (3)	C2—N1—Hg1—Br2	106.8 (14)
C2—C3—C4—C5	176 (2)	C7—N2—Hg1—N1	180 (2)
C3—C4—C5—C6	2 (3)	C3—N2—Hg1—N1	−3.0 (13)
C4—C5—C6—C7	−1 (3)	C7—N2—Hg1—Br1	−63 (2)
C5—C6—C7—N2	−2 (4)	C3—N2—Hg1—Br1	114.5 (14)
O1—C2—N1—Hg1	177.9 (14)	C7—N2—Hg1—Br2	78 (2)
C3—C2—N1—Hg1	0 (2)	C3—N2—Hg1—Br2	−104.9 (14)
C6—C7—N2—C3	3 (3)	N1—Hg1—Br1—Hg3	157.3 (5)
C6—C7—N2—Hg1	−179.3 (17)	N2—Hg1—Br1—Hg3	81.8 (4)
C2—C3—N2—C7	−178.4 (19)	Br2—Hg1—Br1—Hg3	−48.13 (13)
C4—C3—N2—C7	−2 (3)	Br4—Hg3—Br1—Hg1	−102.16 (10)
C2—C3—N2—Hg1	4 (2)	Br5—Hg3—Br1—Hg1	72.22 (8)
C4—C3—N2—Hg1	−179.6 (15)

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

Experimental details

Crystal data
Chemical formula	[Hg₅Br₁₀(C₇H₈N₂O)₂]
M_r	2074.26
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	7.6768 (7), 10.7223 (10), 11.0663 (10)
α, β, γ (°)	92.067 (7), 102.850 (7), 101.879 (7)
V (Å³)	865.86 (14)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	33.65
Crystal size (mm)	0.30 × 0.19 × 0.18

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.105, 0.223
No. of measured, independent and observed [I > 2σ(I)] reflections	7320, 3410, 2042
R_int	0.084
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.062, 0.148, 0.93
No. of reflections	3410
No. of parameters	160
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.89, −1.90

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 2012).

Selected bond lengths (Å) top

Hg1—N1	2.322 (14)	Hg2—Br5	3.189 (2)
Hg1—N2	2.400 (16)	Hg3—Br1	3.119 (2)
Hg1—Br1	2.524 (2)	Hg3—Br2ⁱ	3.140 (2)
Hg1—Br2	2.534 (2)	Hg3—Br3	3.337 (2)
Hg2—Br2	3.204 (2)	Hg3—Br4	2.418 (2)
Hg2—Br3	2.438 (2)	Hg3—Br5	2.463 (2)

Symmetry code: (i) x+1, y, z.

Acknowledgements

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

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