Home Physical Sciences Crystal structure of poly[tetrakis(μ2-cyanido-κ2N:O)-cyanido-tris(pyridine)dicobalt(II/III)], C20H15Co2N8
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Crystal structure of poly[tetrakis(μ2-cyanido-κ2N:O)-cyanido-tris(pyridine)dicobalt(II/III)], C20H15Co2N8

  • Guojie Yin EMAIL logo , Shaowen Zhang , Shimin Wang , Bin Zhang and Yingxiao Wang
Published/Copyright: May 31, 2017

Abstract

C20H15Co2N8, monoclinic, P21/c (no. 14), a = 7.2692(3) Å, b = 20.5546(10) Å, c = 13.7394(6) Å, β = 90.001(1)°, V = 2052.88(16) Å3, Z = 4, Rgt(F) = 0.0415, wRref(F2) = 0.0822, T = 173K.

CCDC no.:: 1548249

The asymmetric unit of the title crystal structure is shown in the figure. Tables 1 and 2 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.

Table 1

Data collection and handling.

Crystal:Dark block
Size:0.40 × 0.20 × 0.10 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:16.4 cm−1
Diffractometer, scan mode:Bruker APEX-II, φ and ω
2θmax, completeness:55.2°, >99%
N(hkl)measured, N(hkl)unique, Rint:38899, 4733, 0.086
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 3707
N(param)refined:271
Programs:Bruker programs [1], SHELX [2]
Table 2

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).

AtomxyzUiso*/Ueq
Co1−0.02936(5)0.29304(2)0.45080(3)0.01476(10)
Co20.47012(5)0.27727(2)0.70399(2)0.01313(9)
N10.1728(3)0.31319(12)0.55828(17)0.0229(5)
N20.4536(3)0.18706(11)0.64985(17)0.0210(5)
N30.7674(3)0.23054(12)0.84465(17)0.0237(5)
N40.7581(3)0.31177(12)0.55282(18)0.0246(5)
N50.1793(3)0.23610(12)0.85145(17)0.0231(5)
N60.5016(5)0.41564(15)0.7760(2)0.0483(8)
N7−0.0412(3)0.19316(12)0.50096(18)0.0254(5)
N8−0.0259(4)0.39427(12)0.40676(18)0.0274(6)
C10.2830(4)0.30334(13)0.61566(19)0.0170(5)
C20.4476(5)0.13548(16)0.7088(3)0.0342(8)
H20.45730.14270.77690.041*
C30.4284(5)0.07263(17)0.6769(3)0.0465(10)
H30.42850.03730.72150.056*
C40.4090(6)0.06231(19)0.5792(3)0.0555(12)
H40.39140.01950.55500.067*
C50.4150(5)0.11398(19)0.5160(3)0.0474(10)
H50.40270.10750.44790.057*
C60.4395(4)0.17587(16)0.5540(2)0.0322(7)
H60.44650.21170.51040.039*
C70.6574(4)0.24968(13)0.79200(19)0.0179(6)
C80.6497(4)0.30015(13)0.61084(19)0.0184(6)
C90.2877(4)0.25461(13)0.79766(19)0.0170(6)
C100.4872(4)0.36275(15)0.7508(2)0.0239(6)
C11−0.0707(5)0.14481(17)0.4386(3)0.0381(8)
H11−0.06740.15420.37090.046*
C12−0.1059(6)0.08161(18)0.4672(3)0.0532(11)
H12−0.12640.04830.42040.064*
C13−0.1104(6)0.0683(2)0.5651(4)0.0589(12)
H13−0.13740.02550.58720.071*
C14−0.0753(5)0.11744(19)0.6315(3)0.0483(10)
H14−0.07350.10890.69950.058*
C15−0.0432(4)0.17884(16)0.5963(2)0.0337(8)
H15−0.02140.21290.64150.040*
C160.1298(6)0.42762(18)0.3982(3)0.0443(9)
H160.24270.40590.41060.053*
C170.1345(8)0.4924(2)0.3719(3)0.0705(15)
H170.24870.51460.36640.085*
C18−0.0272(10)0.5243(2)0.3540(3)0.0824(19)
H18−0.02750.56880.33550.099*
C19−0.1885(8)0.4906(2)0.3631(3)0.0707(14)
H19−0.30300.51140.35110.085*
C20−0.1819(6)0.42647(18)0.3900(3)0.0456(9)
H20−0.29480.40370.39700.055*

Source of materials

Reagents and solvents were of commercially available quality. A solution of cobalt nitrate (0.02911 g, 0.1 mmol) and 1,3-phenylenediacetonitrile (0.03123 g, 0.2 mmol) in distilled water (4 mL) was sealed in a teflon-lined reactor and heated at 403 K for three days, after slow cooling to room temperature, colorless transparent thin crystals were collected and dried in air (yield: 22%, based on Co).

Experimental details

Hydrogen atoms were assigned with Uiso(H) = 1.2 Ueq(C), and included in the final refinement by using geometrical restraints, with d(C—H) = 0.95 Å.

Small ellipsoids for the carbon atoms and significantly larger ellipsoids for the nitrogen atoms of the CN ligand point to a possible disorder. The monoclinic angle is close to 90° but there is no stable refinement in the orthorhombic case.

Comment

One of the biggest barriers of complexes’ application to electroluminescent emission materials is caused by relatively low carrier mobility (especially the electron mobility) [3], just equal to 0.01–0.1% of the traditional LED inorganic material [4]. As a part of this study we have already reported a useful ligand [5]. The title compound has been obtained during a search for complexes with better optical properties.

The environment around both crystallographically independent cobalt atoms of the title compound is a distorted octahedral coordination. Although the Co(II) ions are both six-coordinated, the coordination environment is different. The Co1 atom is six-coordinated [CoN6] in a distorted octahedral manner by six nitrogen atoms from two pyridine rings and four cyano groups. The Co–N bond lengths range from 2.122–2.167 Å and the bond angles of N—Co—N are in the range of 86.15(9)° to 178.04(10)°. The Co2 atom is six-coordinated [CoN1C5] in a distorted octahedral manner and by one nitrogen atom from a pyridine ligand and by five carbon atoms from cyano groups. The Co—N bond length is 2.001 Å, the bond angles surrounding the Co2 atom are in the range of 87.34(12)° to 179.61(12)°. The typical structural characteristic of the title compound is a layer-type coordination polymer. Obviously, the cyano groups play an important role in the structure, especially as bridges between the cobalt atoms. The formation of this compound was unexpected because 1,3-phenylenediacetonitrile was used as educt. The only possibility of this result is that the original ligand molecules have been decomposed into cyano groups and pyridine rings under the condition of high temperature.

Acknowledgement

The author would like to thank the Key Scientific Research Project of Colleges and Universities of Henan Province (No. 15A150061) for financial support.

References

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2 Sheldrick, G. M.: Crystal structure refinement with SHELXL. Acta Crystallogr. C71 (2015) 3–8.10.1107/S2053229614024218Search in Google Scholar

3 Su, H. C.; Fang, F. C.; Hwu, T. Y.; Hsieh, H. H.; Chen, H. F.; Lee, G. H.; Peng, S. M.; Wong, K. T.; Wu, C. C.: Highly efficient orange and green solid-state light-emitting electrochemical cells based on cationic Ir(III) complexes with enhanced steric hindrance. Adv. Funct. Mater. 17 (2007) 1019–1027.10.1002/adfm.200600372Search in Google Scholar

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Received: 2016-12-28
Accepted: 2017-5-6
Published Online: 2017-5-31
Published in Print: 2017-9-26

©2017 Guojie Yin et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

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