Diazido­bis­(5,5′-dimethyl-2,2′-bipyridyl-κ2 N,N′)cobalt(II) monohydrate

Jaturong Phatchimkun; Narongsak Chaichit

doi:10.1107/S1600536811011305

. 2011 Mar 31;67(Pt 4):m516–m517. doi: 10.1107/S1600536811011305

Diazidobis(5,5′-dimethyl-2,2′-bipyridyl-κ² N,N′)cobalt(II) monohydrate

Jaturong Phatchimkun ^a,^*, Narongsak Chaichit ^b

PMCID: PMC3099828 PMID: 21754020

Abstract

In the title compound, [Co(C₁₂H₁₂N₂)₂(N₃)₂]·H₂O, the Co(II) ion is situated on a crystallographic twofold axis and adopts a distorted octahedral geometry with the two dmbpy (dmbpy = 5,5′-dimethyl-2,2′-bipyridyl) and the two azido ligands in a cis arrangement. The solvent water molecule and one methyl group of the dmbpy ligand are disordered over two sets of sites in a 1:1 ratio. The crystal structure is stabilized by intramolecular C—H⋯N(dmbpy) and intermolecular O—H⋯N(azide) hydrogen bonds.

Related literature

For related structures with dmbpy ligands, see: Phatchimkun et al. (2009 ▶); van Albada et al. (2004 ▶, 2005 ▶); Catalan et al. (1995 ▶); Kooijman et al. (2002 ▶). For azido complexes, see: Ribas et al. (1999 ▶) and references therein. For Co—N bond lengths in azido-containing mononuclear Co(II) complexes, see: Cheng & Hu (2003 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

[Co(C₁₂H₁₂N₂)₂(N₃)₂]·H₂O
M _r = 529.46
Orthorhombic,
a = 17.1030 (3) Å
b = 8.5544 (2) Å
c = 16.7062 (5) Å
V = 2444.22 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.74 mm⁻¹
T = 298 K
0.30 × 0.25 × 0.06 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.801, T _max = 0.957
13768 measured reflections
2606 independent reflections
2176 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.024
wR(F ²) = 0.067
S = 1.03
2606 reflections
208 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: COLLECT (Nonius, 2002 ▶); cell refinement: COLLECT and DENZO/SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO/SCALEPACK; 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.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811011305/fj2407sup1.cif

e-67-0m516-sup1.cif^{(19.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811011305/fj2407Isup2.hkl

e-67-0m516-Isup2.hkl^{(127.8KB, hkl)}

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

Table 1. Selected bond lengths (Å).

Co1—N1	2.0907 (11)
Co1—N2	2.0929 (10)
Co1—N3	2.1095 (11)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1O⋯N3ⁱ	1.05 (5)	1.99 (5)	2.926 (3)	141 (4)
C3—H3⋯O1ⁱⁱ	1.00 (2)	2.51 (2)	3.392 (4)	147.1 (14)
C1—H1⋯N3ⁱⁱⁱ	0.991 (15)	2.485 (15)	3.1241 (18)	121.9 (11)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) .

Acknowledgments

The authors would like to thank Vongchavalitkul University for financial support [grant 2/52 (7)] and also gratefully acknowledge Rajamangala University of Technology Isan for support.

supplementary crystallographic information

Comment

Over the last decades, much attention has been paid on azido bridging complexes in the molecule-based magnet research field because azide anion is not only a good bridging ligand for metal ions (such as Cu(II), Ni(II), Mn(II), Co(II) etc) but also an efficient magnetic coupler (Ribas, et al., 1999). On the other hand, azide can act as a monomeric ligand. More than 100 structures of compounds containing the azide anion and cobalt(II) have been reported in the Cambridge Structural Database (CSD; Version 5.29, November 2008 update; Allen, 2002). However, X-ray structures of monomeric compounds with Co^II and azide are very rare. Only 16 crystal structures of cobalt(II) azido monomeric complexes have been reported (CSD code: BAWSIC, FURHEF, GURLEK, HIWDOH, HOVVIX, KAVSIJ, LEXXIW, MIRYAO, MONMAE, OHITTEE, PUBXEQ, RAKFUE, RARHAU, RAZHOP, RETDIE, and RUPTIG). Currently, there is no one report of crystal structure containing Co^II and 5,5'-dimethyl-2,2'-bipyridyl. Here we report on another monomeric compound, namely [Co(dmbpy)₂(N₃)₂]. H₂O, where dmbpy is 5,5'-dimethyl-2,2'-bipyridyl.

It is found that Co ion is coordinated by four nitrogen atoms from dmbpy and two azido nitrogen atoms, taking a distorted octahedral geometry. The two bidentate ligands have a cis disposition around the metal ion, forming practically perpendicular planes [N1–Co–N1ⁱ 89.81 (6), N2–Co–N2ⁱ 175.94 (6)°]. The rigidity of these ligands causes the bond angles N1–Co–N2, 78.12 (4) to deviate significantly from orthogonality. This causes the geometry about the Co^II ion to deviate slightly from that of an ideal octahedron. The Co–N(dmbpy) bond distances in a complex [2.0916 (12) and 2.1091 (13) Å] are almost the same as those found in the Co(II) compound of [Co^II(phen)₂(N₃)₂] (2.067 (2)–2.114 (2) Å) (Cheng & Hu, 2003). Good agreement is observed between the Co–N(azido) bond distance of 2.1091 (13) Å and those reported (Cheng & Hu, 2003) for azido containing mononuclear cobalt(II) complexes. The crystal structure is stabilized by intramolecular C—H···N and intermolecular O—H···N hydrogen bonds (Table 1).

Experimental

Preparation of [Co(dmbpy)₂(N₃)₂]. H₂O. A warm solution of dmbpy (0.181 g, 1.0 mmol) in methanol (15 cm³) was added to a hot aqueous solution (10 cm³) of Co(CH₃COO)₂ (0.123 g, 0.5 mmol). An aqueous solution (10 cm³) of NaN₃ (0.081 g, 1.0 mmol) was then added to the reaction mixture. The pink solution was slowly evaporated at room temperature. Slightly red crystals of [Co(dmbpy)(N₃)₂] were deposited. The crystals were filtered off, washed with mother liquor and air-dried. Yield ca 75%. (Anal. Calc. for C₂₄H₂₆CoN₁₀O (%): C, 54.44; H, 4.95; N, 26.45. Found: C, 54.08; H, 4.72; N, 26.27). IR (in cm^-1): n_as(N₃) 2009 s, n(C—N) 1605 m, n(C—C) 1584 m.