{6,6′-Dimeth­oxy-2,2′-[naphthalene-2,3-diylbis(nitrilo­methyl­idyne)]diphenolato}thio­cyanato­cobalt(III) diethyl ether dichloro­methane solvate

Zhong Yu; Takayoshi Kuroda-Sowa; Atsuhiro Nabei; Masahiko Maekawa; Takashi Okubo

doi:10.1107/S1600536809000841

. 2009 Feb 6;65(Pt 3):m257–m258. doi: 10.1107/S1600536809000841

{6,6′-Dimethoxy-2,2′-[naphthalene-2,3-diylbis(nitrilomethylidyne)]diphenolato}thiocyanatocobalt(III) diethyl ether dichloromethane solvate

Zhong Yu ^a,^b,^*, Takayoshi Kuroda-Sowa ^a, Atsuhiro Nabei ^a, Masahiko Maekawa ^a, Takashi Okubo ^a

PMCID: PMC2968487 PMID: 21582048

Abstract

In the title complex, [Co(C₂₆H₂₀N₂O₄)(NCS)]·C₄H₁₀O·CH₂Cl₂, the pentacoordinated Co^III atom exhibits a distorted square-pyramidal geometry with an N,N′,O,O′ tetradentate Schiff base ligand in the basal plane and one thiocyanate ligand at the apical site. The diethyl ether molecule is located in a cavity provided by four O atoms of the ligand with weak C—H⋯O interactions, generating two short O⋯O contact distances [2.766 (3) and 2.745 (3) Å] between the diethyl ether molecule and the ligand. The crystal structure is stabilized by the weak C—H⋯O and C—H⋯N interactions and π–π interactions between the naphthyl ring system and the benzene ring [centroid–centroid distance = 3.657 (5) Å] and between the two naphthyl ring systems [centroid–centroid distance = 4.305 (2) Å].

Related literature

For the properties of Co(III) complexes with Schiff base ligands, see: Ito & Katsuki (1999 ▶); Wezenberg & Kleij (2008 ▶); Di Bella et al. (1995 ▶). For related structures, see: Kennedy et al. (1984 ▶); Marzilli et al. (1985 ▶); Álvarez et al. (2002 ▶). For hydrogen-bond length data, see: Desiraju & Steiner (1999 ▶). For non-bonded contact distances, see: Rowland & Taylor (1996 ▶); De Angelis et al. (1996 ▶). For the preparation of bis(o-vanillin)-2,3-naphthalenediimine, see: Nabei et al. (2008 ▶).

Experimental

Crystal data

[Co(C₂₆H₂₀N₂O₄)(NCS)]·C₄H₁₀O·CH₂Cl₂
M _r = 700.52
Monoclinic,
a = 9.1935 (9) Å
b = 13.3640 (11) Å
c = 25.910 (3) Å
β = 92.462 (6)°
V = 3180.4 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.82 mm⁻¹
T = 120 (1) K
0.40 × 0.10 × 0.10 mm

Data collection

Rigaku Mercury diffractometer
Absorption correction: multi-scan (Jacobson, 1998 ▶) T _min = 0.799, T _max = 0.921
24340 measured reflections
7241 independent reflections
6234 reflections with I ² > 2σ(I ²)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.075
wR(F ²) = 0.136
S = 1.21
7241 reflections
397 parameters
H-atom parameters constrained
Δρ_max = 0.69 e Å⁻³
Δρ_min = −0.60 e Å⁻³

Data collection: CrystalClear (Rigaku, 2001 ▶); cell refinement: CrystalClear; data reduction: CrystalStructure (Rigaku/MSC, 2007 ▶); program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXL97; software used to prepare material for publication: CrystalStructure.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809000841/is2372sup1.cif

e-65-0m257-sup1.cif^{(30KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000841/is2372Isup2.hkl

e-65-0m257-Isup2.hkl^{(354.3KB, hkl)}

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1⋯N3ⁱ	0.95	2.64	3.579 (4)	172
C28—H28A⋯O2	0.99	2.42	3.352 (4)	157
C29—H29B⋯O4	0.99	2.94	3.424 (4)	111
C30—H30B⋯O3	0.98	2.96	3.607 (5)	125
C32—H32B⋯O2	0.98	2.80	3.453 (4)	124
C32—H32C⋯O1	0.98	2.80	3.423 (4)	122

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported in part by a Grant-in-Aid for Science Research from the Ministry of Education, Science and Culture, Japan (grant No. 18033054). The authors are grateful to Kinki University for financial support. Partial financial support from Xi’an Applied Materials Innovation Fund (grant No. 200713) is also acknowledged.

supplementary crystallographic information

Comment

Cobalt Schiff base complexes have undergone extensive research as a promising catalyst for various homogeneous reactions (Ito & Katsuki, 1999). Since novel solid state properties on structural types, conductive and magnetic properties (Wezenberg & Kleij, 2008; Di Bella et al., 1995), they recently attract new attentions on the material applications. Herein we report a new Co(III) complex based on the Schiff base ligand bis(o-vanillin)-2,3-naphthalenediimine.

In the title complex, the Co(III) ion shows the five-coordinated square pyramidal geometry, which is defined by two N and two O atoms of the tetradentate ligand in the approximate basal plane and one N atoms of thiocyanate in the apical position (Fig. 1). The bond distances and angles associated with Co(III) atoms are comparable with related five-coordinated cobalt species (Kennedy et al., 1984; Marzilli et al., 1985; Álvarez et al., 2002). The ligand plane is distorted with a dihedral angle of 27.81 (12)° between two phenyl rings. The diethyl ether molecule is approximately perpendicular to ligand plane, with the O atom almost coplanar in the ligand.

In the crystal structure, the complex molecule provides a planar cavity of four O atoms which accommodates a diethyl ether molecule via weak C—H···O interactions (Table 1). The range for the H···O distances agree with those found for weak C—H···O hydrogen bonds (Desiraju & Steiner, 1999). There are short non-bonded intramolecular distances between O atoms of diethyl ether and ligand: O1···O5 = 2.766 (3) Å and O2···O5 = 2.745 (3) Å, slightly less than the corresponding van der Waals distances (O···O = 2.80 Å; Rowland & Taylor, 1996). It may be attributed to those weak interactions between diethyl ether and complex, as well as some effects of crystal packing, which is comparable with a distance [Na···O(Me) = 2.54 (3) Å] in a similar structure (De Angelis et al., 1996). The crystal structure is further stabilized by additional interactions C1—H1···N3ⁱand C28—H28A···O2 (Table 2), together with extended π-π interactions between naphthyl rings and phenyl rings [centroid-centroidⁱdistances of 3.657 (5) Å, dihedral angles of 12.97 (10)°] as well as naphthyl rings [centroid-centroidⁱⁱ distances of 4.305 (2) Å, interplanar distances of 3.521 (4) Å] of adjacent molecules [symmetry codes: (i) -x + 2, -y, -z; (ii) -x + 1, -y, -z], forming an infinite three-dimensional network (Fig. 2).

Experimental

The desired ligand, bis(o-vanillin)-2,3-naphthalenediimine, was synthesized according to the literature procedures (Nabei et al., 2008). A solution of Co(SCN)₂ (0.1 mmol, 17.6 mg) in methanol (10 ml) was layered over a solution of ligand (0.1 mmol, 42.6 mg) in dichloromethane (10 ml). After standing for two weeks at room temperature, the brown brick crystals of title complex suitable for X-ray analysis were obtained.