Bis(μ-dithieno[3,2-b:2′,3′-d]thio­phene-2,6-dicarboxyl­ato-κ2 O 2:O 6)bis­[bis­(1,10-phenanthroline-κ2 N,N′)cobalt(II)] dimethyl­formamide disolvate

Christopher M MacNeill; Cynthia S Day; Ronald E Noftle

doi:10.1107/S1600536809011337

. 2009 Apr 8;65(Pt 5):m486. doi: 10.1107/S1600536809011337

Bis(μ-dithieno[3,2-b:2′,3′-d]thiophene-2,6-dicarboxylato-κ² O ²:O ⁶)bis[bis(1,10-phenanthroline-κ² N,N′)cobalt(II)] dimethylformamide disolvate

Christopher M MacNeill ^a, Cynthia S Day ^a, Ronald E Noftle ^a,^*

PMCID: PMC2977552 PMID: 21583738

Abstract

The asymmetric unit of the title compound, [Co₂(C₁₀H₂O₄S₃)₂(C₁₂H₈N₂)₄]·2C₃H₇NO, contains one half of the formula unit, with the rest generated by inversion. The cobalt ion sits in a slightly distorted octahedral environment and is ligated to four N atoms of two 1,10-phenanthroline molecules and to two O atoms of two dithieno[3,2-b:2′,3′-d]thiophene-2,6-dicarboxylate anions. The anions act as bridges between the Co^II centers.

Related literature

For the synthesis of complexes with this ligand, see: Chisholm et al. (2008 ▶). For similar complexes, see: Xiao et al. (2005 ▶); Sun et al. (2005 ▶); Niu et al. (2004 ▶); Poleti et al. (1999 ▶).

Experimental

Crystal data

[Co₂(C₁₀H₂O₄S₃)₂(C₁₂H₈N₂)₄]·2C₃H₇NO
M _r = 1549.52
Triclinic,
a = 9.884 (3) Å
b = 11.492 (3) Å
c = 15.215 (4) Å
α = 91.173 (3)°
β = 105.065 (3)°
γ = 93.057 (3)°
V = 1665.4 (7) Å³
Z = 1
Mo Kα radiation
μ = 0.76 mm⁻¹
T = 193 K
0.12 × 0.10 × 0.04 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2008a ▶) T _min = 0.828, T _max = 0.970
15360 measured reflections
7532 independent reflections
5496 reflections with I > 2σ(I)
R _int = 0.045

Refinement

R[F ² > 2σ(F ²)] = 0.062
wR(F ²) = 0.133
S = 1.06
7532 reflections
462 parameters
H-atom parameters constrained
Δρ_max = 0.62 e Å⁻³
Δρ_min = −0.44 e Å⁻³

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008b ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809011337/pk2151sup1.cif

e-65-0m486-sup1.cif^{(31KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011337/pk2151Isup2.hkl

e-65-0m486-Isup2.hkl^{(368.5KB, hkl)}

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

Acknowledgments

The authors thank the National Science Foundation (grant CHE-0234489) for funds to purchase the X-ray instrument and computers. We also thank the Wake Forest University Science Research Fund for the partial support of this project.

supplementary crystallographic information

Comment

We obtained the title compound during the course of our studies while forming Co^II/1,10 phen/DTTH based coordination polymers. The asymmetric unit of the compound contains one cobalt ion along with one DTTH molecule, two 1,10-phen molecules and one lattice dimethylformamide (DMF) solvent molecule. The dimer consists of two Co(1,10-phen)₂²⁺ cations linked by two bis-monodentate DTTH linkers. Each cobalt(II) ion is six-coordinate, forming a distorted octahedral geometry with the angles around Co1 ranging from 76.8 (1)°-104.1 (1)° and 163.9 (1)° -165.8 (1)°, respectively. Co1 is coordinated by four nitrogen atoms from two 1,10-phen moieties and two oxygen atoms from two bis-monodentate DTTH molecules. The Co—N bond lengths range from 2.127 (3)–2.192 (3)Å while the Co—O bond lengths range from 2.047 (2)–2.097 (2) Å. The angle between planes formed by the two 1,10-phen rings is 76.69 (6)°.

Experimental

The title compound was prepared using a hydrothermal method. A mixture of cobalt nitrate pentahydrate (1.7 mmol), dithieno[3,2 - b:2',3'-d]thiophene-2,6-dicarboxylic acid (1.8 mmol) and 1,10-phenanthroline (5 mmol) were added to a vial containing DMF (1 ml) and EtOH (0.2 ml). The vial was capped and set in an oven at 105°C for 2 d. The vial was slowly cooled to room temperature to yield pink gem-like crystals.