Poly[[[diisothio­cyanato­cobalt(II)]-bis­[μ-4-tert-butyl-2,6-bis­(1,2,4-triazol-1-ylmeth­yl)phenol]] dimethyl­formamide disolvate dihydrate]

Zhao-lian Chu

doi:10.1107/S1600536809005121

. 2009 Feb 18;65(Pt 3):m288. doi: 10.1107/S1600536809005121

Poly[[[diisothiocyanatocobalt(II)]-bis[μ-4-tert-butyl-2,6-bis(1,2,4-triazol-1-ylmethyl)phenol]] dimethylformamide disolvate dihydrate]

Zhao-lian Chu ^a,^*

PMCID: PMC2968591 PMID: 21582072

Abstract

In the title compound, {[Co(NCS)₂(C₁₆H₂₀N₆O)₂]·2C₃H₇NO·2H₂O}_n, each Co^II ion located on an inversion center is six-coordinated by four equatorial N atoms from four different 4-tert-butyl-2,6-bis(1,2,4-triazol-1-ylmethyl)phenol (L) ligands, and by two N atoms from two axial thiocyanate anions [Co—N = 2.104 (3)–2.144 (3) Å]. The metal centres are connected via the bidentate L ligands into two-dimensional polymeric layers parallel to bc plane. The dimethylformamide and solvent water molecules participate in intermolecular O—H⋯O and O—H⋯S hydrogen bonds, which consolidate the crystal packing.

Related literature

For related structures, see: Chu et al. (2007 ▶, 2008 ▶); Ma et al. (2003 ▶); Zhu et al. (2004 ▶, 2007 ▶). For details of the synthesis, see Yan et al. (1994 ▶).

Experimental

Crystal data

[Co(NCS)₂(C₁₆H₂₀N₆O)₂]·2C₃H₇NO·2H₂O
M _r = 982.07
Monoclinic,
a = 12.561 (4) Å
b = 20.660 (6) Å
c = 10.571 (3) Å
β = 112.992 (5)°
V = 2525.2 (12) Å³
Z = 2
Mo Kα radiation
μ = 0.48 mm⁻¹
T = 291 K
0.30 × 0.30 × 0.20 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.869, T _max = 0.910
13505 measured reflections
4950 independent reflections
2902 reflections with I > 2σ(I)
R _int = 0.057

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.123
S = 0.90
4950 reflections
301 parameters
H-atom parameters constrained
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.28 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: SHELXTL (Sheldrick, 2008 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809005121/cv2519sup1.cif

e-65-0m288-sup1.cif^{(21.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809005121/cv2519Isup2.hkl

e-65-0m288-Isup2.hkl^{(242.5KB, 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
O1—H1⋯O2	0.82	1.94	2.689 (4)	152
O2—H2A⋯O3	0.85	1.81	2.655 (5)	179
O2—H2B⋯S1ⁱ	0.85	2.51	3.321 (3)	161

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Symmetry code: (i) Inline graphic .

Acknowledgments

The author acknowledges Anhui University of Technology for supporting this work.

supplementary crystallographic information

Comment

Ligand 2,6-bis(1,2,4-triazol-1-ylmethyl)-4-tert-butyl-phenol (bttp) has been used to generate various metal-organic architectures with different transitional metal ions due to its polydentate character and bridging ability (Chu et al., 2007, 2008; Ma et al., 2003; Zhu et al., 2004, 2007). As a further study of such complexes, the title Co^II complex is reported in this paper.

Each Co^II atom exhibits a slightly distorted octahedral environment with four nitrogen atoms from the triazole groups of four bttp ligands in the equatorial plane, and two nitrogen atoms from two thiocyanate ligands at the axial positions (Fig. 1). Each ligand adopts a cis conformation in which two triazole groups are on the same direction of the central phenyl ring. The dihedral angles between the phenyl ring and the two triazole rings are 97.8 (3) ° and 88.8 (3) °, respectively. The two triazole rings are inclined to one another, with a dihedral angle of 65.3 (3) °. Each bttp serves as a bidentate bridging ligand via two exodentate nitrogen atoms at the 4-position of the triazole rings while the nitrogen atoms at 1,2-positions remain uncoordinated. In this way four metal atoms and four bttp ligands form a 48-membered [M₄L₄] metallocyclic ring, which is further assembled into a two-dimensional network via Co–N coordination bonds (Fig. 2). The Co···Co distance linked by the bridged bttp ligand is 11.604 (1) Å. The water oxygen atom is uncoordinated, and contributes to the formation of O–H···O and O–H···S hydrogen-bonding interactions with phenol group and DMF molecule (Table 1).

Experimental

All solvents and chemicals were of analytical grade and were used without further purification. Ligand bttp was prepared via a one-step Mannich reaction as a white powder in 57% yield (Yan et al., 1994). For the synthesis of title compoud, a solution of bttp (0.1 mmol), Co(NO₃)₂.6H₂O (0.1 mmol) and NH₄SCN (0.25 mmol) in 30 ml e thanol was refluxed for 2 h, and then cooled to room temperature and filtered. The collected solid was dissolved in 1 ml DMF, and 20 ml e thanol was added to this solution. The mixture was left to stand at room temperature for two weeks and pink crystalline products were obtained (30.5 mg, 62%). Anal. Calcd. for C₄₀H₅₈CoN₁₆O₆S₂: C, 48.92; H, 5.95; N, 22.82. Found: C, 48.88; H, 5.98; N, 22.72.