Dicyanido[tris­(2-pyridyl­meth­yl)amine]­cobalt(III) hexa­fluorido­phosphate

Fan Yu; Bao Li

doi:10.1107/S1600536811012001

. 2011 Apr 13;67(Pt 5):m566. doi: 10.1107/S1600536811012001

Dicyanido[tris(2-pyridylmethyl)amine]cobalt(III) hexafluoridophosphate

Fan Yu ^a,^*, Bao Li ^b

PMCID: PMC3089135 PMID: 21754296

Abstract

In the title complex, [Co(CN)₂(C₁₈H₁₈N₄)]PF₆, the Co^III atom together with one of the pyridyl rings and two cyanide anions are located on a mirror plane, while the P atom is located on an inversion centre. The Co^III atom exhibits an octahedral geometry, coordinated by four N atoms from the tris(2-pyridylmethyl)amine ligand with an average Co—N distance of 1.953 (2) Å, and two cyanide C atoms with an average Co—C distance of 1.895 (2) Å. The crystal packing is stabilized by intermolecular C—H⋯N and C—H⋯F interactions.

Related literature

For related structures, see: Guo et al. (2007 ▶), Liu et al. (2010 ▶).

Experimental

Crystal data

[Co(CN)₂(C₁₈H₁₈N₄)]PF₆
M _r = 546.30
Orthorhombic,
a = 10.703 (2) Å
b = 13.472 (3) Å
c = 15.151 (3) Å
V = 2184.7 (8) Å³
Z = 4
Mo Kα radiation
μ = 0.93 mm⁻¹
T = 293 K
0.40 × 0.30 × 0.25 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.722, T _max = 0.792
26914 measured reflections
2173 independent reflections
2053 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.070
S = 1.08
2173 reflections
176 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: SMART (Bruker, 1997 ▶); cell refinement: SAINT (Bruker, 1999 ▶); data reduction: SAINT; 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 (Sheldrick, 2008 ▶).

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811012001/vm2083sup1.cif

e-67-0m566-sup1.cif^{(20.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012001/vm2083Isup2.hkl

e-67-0m566-Isup2.hkl^{(109.1KB, 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
C3—H3A⋯N4ⁱ	0.93	2.60	3.339 (3)	137
C6—H6A⋯F3ⁱ	0.96	2.29	3.234 (2)	169
C7—H7A⋯F2ⁱⁱ	0.93	2.44	3.128 (3)	131
C9—H9A⋯N5ⁱⁱⁱ	0.93	2.57	3.410 (2)	151

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

Acknowledgments

Jianghan University and Huazhong University of Science and Technology are thanked for their generous financial support and for a start-up grant.

supplementary crystallographic information

Comment

Transitional metal-cyanide systems have been extensively investigated due to their versatile structure and physical properties, especially in the field of molecular-based magnets. A large number of cyanide-bridged heterobimetallic or homometallic coordination complexes that exhibit excellent magnetic properties has been constructed by using the hexacyanoferrate(III) and hexacyanocobaltate(III) anions as templates (Liu et al., 2010). In constrast, complexes constructed by using the octacyanotungsten(IV) anion are rare. In an attempt to synthesize new complexes, we decided to use octacyanotungsten(IV) anions as template and new compounds containing cyanides have been obtained. The octacyanotungsten(IV) anion was not coordinated to Co atom via cyanide bridges, but acts as source of in situ cyanide generation.

In the title compound, the cobalt(III) centers are coordinated by two cyanides and tris(2-pyridylmethyl)amine (Fig. 1). Each cobalt(III) ion is coordinated by four N atoms with average Co—N distance of 1.957 (2) Å and two C atoms with average Co—C distance of 1.895 (2) Å in a rigid octahedral geometry, in accordance with those observed in other [Co(N)₄(CN)₂]^- units (Guo et al., 2007). The dihedral angle of two types of pyridyl rings is about 80.17°, indicating the nearly perpendicular occupation of these pyridyl rings. The crystal packing is stabilized by C—H···N and C—H···F hydrogen bonding interactons (Table 1, Fig. 2).

Experimental

0.01 mmol K₄W(CN)₈ in 5 ml H₂O was added in a tube, and 3 ml H₂O was layered on as a buffer. A solution containing 0.1 mmol CoCl₂.6H₂O, 0.11 mmol tris(2-pyridylmethyl)amine and 0.11 mmol KPF₆ in 5 mL acetone and 1 ml H₂O was stirred for 30 min and layered on top of the previous solution. After half a year, yellow crystals were obtained.