μ-2,3,5,6-Tetra-2-pyridylpyrazine-κ3 N 1,N 2,N 6:κ3 N 3,N 4,N 5-bis­[(methanol-κO)(nitrato-κ2 O,O′)(nitrato-κO)cadmium(II)]

Mirabdullah Seyed Sadjadi; Amin Ebadi; Karim Zare; Vahid Amani; Hamid Reza Khavasi

doi:10.1107/S1600536808022320

. 2008 Jul 19;64(Pt 8):m1050–m1051. doi: 10.1107/S1600536808022320

μ-2,3,5,6-Tetra-2-pyridylpyrazine-κ³ N ¹,N ²,N ⁶:κ³ N ³,N ⁴,N ⁵-bis[(methanol-κO)(nitrato-κ² O,O′)(nitrato-κO)cadmium(II)]

Mirabdullah Seyed Sadjadi ^a,^*, Amin Ebadi ^a, Karim Zare ^b, Vahid Amani ^c, Hamid Reza Khavasi ^b

PMCID: PMC2961967 PMID: 21203037

Abstract

The title complex, [Cd₂(NO₃)₄(C₂₄H₁₆N₆)(CH₄O)₂], displays a centrosymmetric dinuclear structure, in which the 2,3,5,6-tetra-2-pyridinylpyrazine (tppz) ligand links two Cd ions separated by 7.323 (4) Å. Each Cd^II center is seven-coordinated by three N-atom donors of tppz in one plane, by two O atoms nearly normal to this plane, and by two O atoms 0.393 (3) and 0.488 (3) Å from that plane. The two Cd^II ions are above and below the plane of the pyrazine ring of the tppz ligand, oriented with respect to the pyridine rings at dihedral angles of 38.01 (3) and 31.90 (3)°. The dihedral angle between the two pyridine rings is 41.11 (3)°. In the crystal structure, intermolecular O—H⋯O hydrogen bonds link the molecules.

Related literature

For related literature, see: Bock et al. (1992 ▶); Carranza et al. (2004 ▶); Goodwin & Lyons (1959 ▶); Graf et al. (1993 ▶, 1997 ▶); Greaves & Stoeckli-Evans (1992 ▶); Hadadzadeh et al. (2006 ▶); Laine et al. (1995 ▶); Sakai & Kurashima (2003 ▶); Yamada et al. (2000 ▶); Zhang et al. (2005 ▶).

Experimental

Crystal data

[Cd₂(NO₃)₄(C₂₄H₁₆N₆)(CH₄O)₂]
M _r = 925.37
Monoclinic,
a = 9.0777 (12) Å
b = 10.8949 (9) Å
c = 16.690 (2) Å
β = 93.847 (10)°
V = 1646.9 (3) Å³
Z = 2
Mo Kα radiation
μ = 1.38 mm⁻¹
T = 298 (2) K
0.50 × 0.40 × 0.25 mm

Data collection

Stoe IPDSII diffractometer
Absorption correction: numerical (X-SHAPE; Stoe & Cie, 2005 ▶) T _min = 0.510, T _max = 0.710
4664 measured reflections
4642 independent reflections
4223 reflections with I > 2σ(I)
R _int = 0.075

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.171
S = 1.07
4642 reflections
239 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.00 e Å⁻³
Δρ_min = −0.95 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2005 ▶); cell refinement: X-AREA; data reduction: X-RED (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 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808022320/hk2497sup1.cif

e-64-m1050-sup1.cif^{(22.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808022320/hk2497Isup2.hkl

e-64-m1050-Isup2.hkl^{(170.2KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Selected geometric parameters (Å, °).

O1—Cd1	2.330 (4)
O2—Cd1	2.431 (4)
O3—Cd1	2.476 (4)
O5—Cd1	2.305 (4)
N1—Cd1	2.407 (4)
N2—Cd1	2.359 (4)
N3—Cd1	2.393 (4)

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O5—Cd1—O1	150.47 (16)
O5—Cd1—N2	119.29 (16)
O1—Cd1—N2	88.94 (13)
O5—Cd1—N3	94.10 (16)
O1—Cd1—N3	87.79 (13)
N2—Cd1—N3	69.31 (13)
O5—Cd1—N1	106.73 (17)
O1—Cd1—N1	90.37 (14)
N2—Cd1—N1	69.73 (12)
N3—Cd1—N1	139.02 (13)
O5—Cd1—O2	77.34 (15)
O1—Cd1—O2	81.82 (14)
N2—Cd1—O2	149.55 (11)
N3—Cd1—O2	138.56 (14)
N1—Cd1—O2	81.32 (12)
O5—Cd1—O3	72.18 (16)
O1—Cd1—O3	78.57 (14)
N2—Cd1—O3	152.93 (12)
N3—Cd1—O3	86.13 (13)
N1—Cd1—O3	133.44 (13)
O2—Cd1—O3	52.52 (12)

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Table 2. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1B⋯O3ⁱ	0.92 (5)	1.87 (5)	2.788 (5)	172

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Symmetry code: (i) Inline graphic .

Acknowledgments

We are grateful to the Science and Research Campus, Islamic Azad University, Poonak, and Shahid Beheshti University for financial support

supplementary crystallographic information

Comment

Goodwin & Lyons (1959) were reported the synthesis of 2,3,5,6-tetra- (2-pyridinyl)pyrazine (tppz). Bock et al. (1992) and Greaves & Stoeckli-Evans (1992) were determined the structure of tppz by single crystal X-ray analysis. Among many reported compounds containing tppz, most are complexes of transition metal ions, including ruthenium (Hadadzadeh et al., 2006), platinum (Sakai & Kurashima, 2003), mercury (Zhang et al., 2005), copper (Carranza et al., 2004), iron (Laine et al., 1995), nickel (Graf et al., 1997), palladium (Yamada et al., 2000) and zinc (Graf et al., 1993). For further investigation of 2,3,5,6-tetra(2-pyridinyl)pyrazine, we synthesized the title complex, and report herein its crystal structure.

The title complex is a centrosymmetric dinuclear complex, in which the tppz ligand link two Cd ions separated by 7.323 (4) Å (Fig. 1). Each Cd^II center is seven-coordinated by three N donors of tppz in one plane, two O atoms (O1 and O5) nearly normal to this plane (Table 1) and two O atoms -0.393 (3) Å (for O2) and -0.488 (3) Å (for O3) away from that plane. The two Cd^II ions are above and below the plane of the pyrazine ring B (N2/C6/C7/N2a/C6a/C7a) [symmetry code: (a) 1 - x, -y, -z] of the tppz ligand. The dihedral angles between rings A (N1/C1-C5), B and C (N3/C8-C12) are A/B = 38.01 (3)°, A/C = 41.11 (3)° and B/C = 31.90 (3)°.

In the crystal structure, intermolecular O-H···O hydrogen bonds (Table 2) link the molecules (Fig. 2), in which they may be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, a solution of 2,3,5,6-tetra- (2-pyridinyl)pyrazine (0.4 g, 1 mmol) in HCl₃ (30 ml) was added to a solution of Cd(NO₃)₂.4H₂O (0.62 g, 2 mmol) in methanol (200 ml) and the resulting colorless solution was stirred for 15 min at room temperature. Then, it was left to evaporate slowly at room temperature. After one week, colorless prismatic crystals of the title compound were isolated (yield; 0.71 g, 76.73%, m.p < 573 k).