Crystal structure of poly[[μ-1,1′-(butane-1,4-di­yl)bis­(1H-benzimidazole)-κ2 N 3:N 3′]{μ-4,4′-[1,4-phenyl­enebis(­oxy)]di­ben­zo­ato-κ4 O,O′:O′′,O′′′}cobalt(II)]

Chen Xie; ChangGe Zheng

doi:10.1107/S2056989015008294

. 2015 May 20;71(Pt 6):m131–m132. doi: 10.1107/S2056989015008294

Crystal structure of poly[[μ-1,1′-(butane-1,4-diyl)bis(1H-benzimidazole)-κ² N ³:N ^3′]{μ-4,4′-[1,4-phenylenebis(oxy)]dibenzoato-κ⁴ O,O′:O′′,O′′′}cobalt(II)]

Chen Xie ^a, ChangGe Zheng ^a,^*

PMCID: PMC4459380 PMID: 26090167

Abstract

In the title compound, [Co(C₂₀H₁₂O₆)(C₁₈H₁₈N₄)]_n, the Co^II atom, located on a twofold rotation axis, is hexacoordinated to four O from two bis-bidentate 4,4′-[phenylenebis(oxy)]dibenzoate (L) ligands and two N atoms from two 1,1′-(butane-1,4-diyl)bis(1H-benzimidazole) (bbbm) ligands, forming a distorted octahedral cis-N₂O₄ coordination environment. Polymeric zigzag chains along [102] are built up by the bridging L ligands. These chains are additionally connected by the bbbm ligands to produce a two-dimensional coordination polymer parallel too (010).

Keywords: crystal structure, metal–organic frameworks, bis-benzimidazole, dicarboxylate

Related literature

As a result of their intriguing variety of architectures and topologies, metal–organic frameworks (MOFs) with transition metal Co have received extensive interest. Bis-benzimidazole ligands bearing with butyl spacers are a good choice for the assembly of versatile entangled structures, see: Liu et al. (2008 ▸). Complexes with dicarboxylate ligands represent the most reliable and typical building blocks which can be jointly applied to synthesize a wide range of compounds with coordination networks, see: Du et al. (2013 ▸). For the potential properties of metal–organic complexes involving polycarboxylate ligands or bis-benzimidazole, see: Li et al. (2011 ▸); Wang et al. (2004 ▸); Sun et al. (2009 ▸); Wang et al. (2005 ▸); Łyszczek & Mazur (2012 ▸); Meng et al. (2003 ▸). graphic file with name e-71-0m131-scheme1.jpg

Experimental

Crystal data

[Co(C₂₀H₁₂O₆)(C₁₈H₁₈N₄)]
M _r = 697.59
Monoclinic,
a = 16.961 (4) Å
b = 16.446 (3) Å
c = 12.987 (3) Å
β = 117.022 (3)°
V = 3227.1 (12) Å³
Z = 4
Mo Kα radiation
μ = 0.59 mm⁻¹
T = 296 K
0.27 × 0.24 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2007 ▸) T _min = 0.858, T _max = 0.897
7207 measured reflections
2836 independent reflections
2385 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.140
S = 1.02
2836 reflections
222 parameters
H-atom parameters constrained
Δρ_max = 0.61 e Å⁻³
Δρ_min = −0.65 e Å⁻³

Data collection: APEX2 (Bruker, 2007 ▸); cell refinement: SAINT (Bruker, 2007 ▸); 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.

Supplementary Material

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989015008294/im2463sup1.cif

e-71-0m131-sup1.cif^{(25.7KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015008294/im2463Isup2.hkl

e-71-0m131-Isup2.hkl^{(139.3KB, hkl)}

Click here for additional data file.^{(23.5KB, tif)}

20 12 6 18 18 4 n . DOI: 10.1107/S2056989015008294/im2463fig1.tif

The molecular structure of [Co(C₂₀H₁₂O₆)(C₁₈H₁₈N₄)]_n, with the non-H atom-numbering scheme and 30% probability displacement ellipsoids.

Click here for additional data file.^{(32.8KB, tif)}

20 12 6 18 18 4 n . DOI: 10.1107/S2056989015008294/im2463fig2.tif

Three-dimensional network structure of [Co(C₂₀H₁₂O₆)(C₁₈H₁₈N₄)]_n formed by C—H–O interaction.

CCDC reference: 1045681

Additional supporting information: crystallographic information; 3D view; checkCIF report

Acknowledgments

The authers thank NanJing University for the single-crystal X-ray diffraction determination.

supplementary crystallographic information

S1. Comment

Because of the intriguing varieties of architectures and topologies, metal-organic frameworks (MOFs) with transition-metal Co have received extensive interests. The bis-benzimidazole ligands bearing with butyl spacers are a good choice for the assembly of versatile entangled structures. (Ying-Ying Liu et al., 2008) Complexes with the dicarboxylate ligands represent the most reliable and typical building blocks which can be jointly applied to synthesize a wide range of desired coordination networks (Du et al., 2013).

Single-crystal X-ray diffraction analyses reveal that Co(II) is six-coordinate. The asymmetric unit contains one Co(II) atom, a dicarboxylate ligand and a bbbm ligand. Two carboxylate groups adopt a chelating bidentate mode to connect one Co(II) atoms. The Co—O bond length is 2.3705 (24)Å (O1) and 2.0422 (21)Å (O2), the Co—N bond length is 2.0797 (26)Å.

S2. Synthesis and crystallization

A mixture of 1,4-bis(4-carboxylphenoxy)benzene (0.035 g, 0.1 mmol), 1,1'-(1,4-butyl) bis-benzimidazole (0.029 g, 0.1 mmol), Co(NO₃)₂ H₂O (0.029 g, 0.1 mmol), and deionized water (9 mL) was stired for 10 min at ambient temperature. Then the mixture was sealed in a Teflon-lined stainless vessel(25 mL) and heated at 160 °C for 3 days. The vessel was cooled to 50 °C by 9 °C decrease per hour, then cooled to ambient temperature directly. Amaranth transparent block-like crystal were obtained by fitretion and washed with deionized water. Yield: 34.2 mg(49 %, based on Co) Elemental analysis (%) calcd. for CoC₃₈H₃₀N₄O₆: C 65.33, H 4.3, N 8.02. Found: C 65.38, H 4.39, N 8.11.

S3. Refinement

The H atoms bonded to C atoms were introduced at calculated positions and refined using a riding model, with U_iso(H) = 1.2U_eq(C) and C–H distances of 0.93–0.97 Å.