Bis(2,2′:6′,2′′-terpyridine)cobalt(II) bis­(tricyano­methanide)

Jun Luo; Xin-Rong Zhang; Li-Juan Qiu; Bao-Shu Liu; Zhi-Yan Zhang

doi:10.1107/S160053680901071X

. 2009 Mar 28;65(Pt 4):m455–m456. doi: 10.1107/S160053680901071X

Bis(2,2′:6′,2′′-terpyridine)cobalt(II) bis(tricyanomethanide)

Jun Luo ^a, Xin-Rong Zhang ^a,^*, Li-Juan Qiu ^a, Bao-Shu Liu ^a, Zhi-Yan Zhang ^b

PMCID: PMC2968836 PMID: 21582390

Abstract

The title complex, [Co(C₁₅H₁₁N₃)₂](C₄N₃)₂, is built up from discrete [Co(terpy)₂]²⁺ cations (terpy is 2,2′:6′,2′′-terpyridine) and [C(CN)₃]⁻ anions. In the cation, the Co^II atom is coordinated by two terpy molecules, giving a distorted octahedral geometry. The tricyanomethanide anions are not directly coordinated to the Co^II atom, but some weak C—H⋯N hydrogen bonds involving the terminal N atoms of the tricyaomethanide ions and the terpyridine H atoms link anions and cations building a three-dimensional network.

Related literature

For the structural characteristics and magnetic properties of tricyanomethanide coordination polymers, see: Batten et al. (1998 ▶, 2000 ▶); Batten & Murray (2003 ▶); Miller & Manson (2001 ▶); Manson et al. (1998 ▶, 2000 ▶); Manson & Schlueter (2004 ▶); Feyerherm et al. (2003 ▶, 2004 ▶); Abrahams et al. (2003 ▶); Hoshino et al. (1999 ▶); Yuste et al. (2008 ▶); Luo et al. (2008 ▶). For Co—N(terpy) distances in other cobalt–terpyridine complexes, see: Indumathy et al. (2007 ▶). For bond distances and bond angles in other tricyanomethanide complexes, see: Hoshino et al. (1999 ▶); Batten et al. (1999 ▶). For weak C—H⋯N interactions, see: Nardelli (1995 ▶).

Experimental

Crystal data

[Co(C₁₅H₁₁N₃)₂](C₄N₃)₂
M _r = 705.61
Monoclinic,
a = 9.042 (3) Å
b = 9.167 (3) Å
c = 40.340 (14) Å
β = 91.163 (6)°
V = 3343 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.56 mm⁻¹
T = 293 K
0.20 × 0.15 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.896, T _max = 0.946
13582 measured reflections
5880 independent reflections
3009 reflections with I > 2σ(I)
R _int = 0.093

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.106
S = 0.96
5880 reflections
460 parameters
H-atom parameters constrained
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053680901071X/dn2438sup1.cif

e-65-0m455-sup1.cif^{(24.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680901071X/dn2438Isup2.hkl

e-65-0m455-Isup2.hkl^{(287.9KB, 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
C4—H4⋯N7	0.93	2.74	3.589 (7)	153
C8—H8⋯N9	0.93	2.71	3.347 (8)	126
C15—H15⋯N11	0.93	2.55	3.254 (6)	133
C1—H1⋯N12ⁱ	0.93	2.85	3.598 (6)	138
C23—H23⋯N11ⁱ	0.93	2.89	3.622 (6)	136
C2—H2⋯N10ⁱⁱ	0.93	2.77	3.670 (7)	164
C29—H29⋯N9ⁱⁱⁱ	0.93	2.85	3.560 (8)	134
C17—H17⋯N8^iv	0.93	2.65	3.395 (7)	137
C13—H13⋯N8^v	0.93	2.65	3.379 (7)	136
C18—H18⋯N12^vi	0.93	2.69	3.403 (6)	134
C22—H22⋯N10^vi	0.93	2.51	3.231 (6)	134
C19—H19⋯N12^vii	0.93	2.96	3.679 (6)	135
C22—H22⋯N12^vii	0.93	2.92	3.645 (6)	136
C24—H24⋯N10^viii	0.93	2.67	3.548 (6)	158
C27—H27⋯N10^viii	0.93	2.57	3.350 (6)	142

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) ; (vi) ; (vii) ; (viii) .

Acknowledgments

This project is supported by the National Natural Science Foundation of China (20571086).

supplementary crystallographic information

Comment

Recently, coordination polymers constructed by tricyanomethanide (tcm) have attracted considerable interest due to their unique structure characteristics and fascinating magnetic properties (Batten et al., 2003; Miller et al., 2001; Feyerherm et al., 2003). Interestingly, most binary tcm complexes reveal a rutile-like structure (Manson et al., 2000, 1998; Hoshino et al., 1999; Feyerherm et al., 2004), except that a doubly interpenetrated (6,3) sheet was detected in Ag(tcm)₂ (Abrahams et al., 2003). To elucidate the structure-properties relationship of tcm complexes, diverse co-ligands such as hexamethylenetetramine, 4,4-bipyridyl, 1,2-bi(4-pyridyl)ethane were introduced and the structures as well as magnetic properties of the modified complexes have been systematically investigated. Among the Cu(I) or Cd(II) tcm complexes with these co-ligands, numerous structure types range from doubly interpenetrated (4,4) sheet to three-dimensional rutile networks were observed (Batten et al., 2000, 1998). By contrast, adjustment of the Mn(II)-tcm binary system with 4,4-bipyridyl as co-ligands leads to the formation of a one dimensional chain-like structure (Manson et al., 2004). On the other hand, 2,2':6'2''-terpyridine (terpy) has three potential nitrogen donor atoms. However, a few tcm complexes with terpy as a co-ligand have ever been reported (Yuste et al., 2008; Luo et al., 2008). To further study the role of the nature of co-ligands on the structures and properties of tricyanomethanide complexes, we herein report the synthesis and crystal structure of the new tricyanomethanide complex [Co(terpy)₂](C₄N₃) ₂ (I).

In I the cobalt ion is bonded to six N atoms from two terpyridine molecules to define the cation part, in which the basal plane is formed by the three N atoms (N1, N2, N3) of one terpy ligand and one N atom (N5) of the other terpy ligand, the apical sites are occupied by two N atoms (N4 and N6) of the latter terpy ligand. The tricyanomethanide anions do not enter the inner coordination sphere, but are linked to the cation part via weak C-H···N interactions (Fig. 1). These weak C-H···N interactions (Nardelli, 1995) build up a three dimensional network (Table 1).

In I, the Co—N(terpy) distances are in the range from 1.858 (3)Å to 2.139 (3) Å, these value are similar to the corresponding distances observed in other cobalt-terpyridine complexes (Indumathy et al., 2007).

Each tricyanomethanide moiety is almost planar. Bond distances and bond angles within the anions are in good agreement with those found in other tricyanomethanide complexes (Hoshino et al., 1999; Batten et al., 1999).

Experimental

A 5 ml e thanol solution of terpyridine (0.10 mmol, 23.33 mg) and a 2 ml aqueous pink solution of cobalt nitrate (0.10 mmol, 29.10 mg) were mixed and stirred for 5 min, the mixed solution was deep-brown. To the mixture was added a 3 ml e thanol-water solution (EtOH:H₂O = 2:1, V:V) of potassium tricyanomethanide (0.20 mmol, 25.83 mg). After stirring for another 5 min, the deep-brown solution was filtered and the filtrate was slowly evaporated in air. After two week, deep-brown block crystals of I were isolated in 17% yield. Anal: Calculated for C38H22CoN12: C 64.68%, H 3.14%, N 23.82%. Found C 64.84%, H 3.22%, N 23.95%.