Home Crystal structure of [6,6′-(((2,2-dimethylpropane-1,3-diyl)bis(azanylylidene))bis(methanylylidene))bis(2-chlorophenolato)-κ4N,N′,O,O′]copper(II)
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Crystal structure of [6,6′-(((2,2-dimethylpropane-1,3-diyl)bis(azanylylidene))bis(methanylylidene))bis(2-chlorophenolato)-κ4N,N′,O,O′]copper(II)

  • Rui Duan , Xun Ma , Meifen Huang , Man Wang and Qiong Wu ORCID logo EMAIL logo
Published/Copyright: November 17, 2021

Abstract

C19H18Cl2CuN2O2, monoclinic, space group C2/c (no. 15), a = 21.010(3) Å, b = 11.3886(15) Å, c = 7.9578(10) Å, β = 100.725(4)°, V = 1870.8(4) Å3, Z = 4, wR 2 = 0.1620, T = 170.0 K.

CCDC no.: 2112999

The molecular structure is shown in the figure. Table 1 contains crystallographic data and Table 2 contains the list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal: Block, clear greenish black
Size 0.20 × 0.14 × 0.12 mm
Wavelength: Mo Kα radiation (0.71073 Å)
μ: 1.47 mm−1
Diffractometer, scan mode: Xcalibur, φ and ω-scans
θ max, completeness: 26.5°, >99%
N(hkl) measured , N(hkl) unique, Rint: Rint: 8248, 1902, 0.100
Criterion for I obs, N(hkl) gt: I obs > 2 σ(I obs), 1526
N(param) refined: 120
Programs: CrysAlisPRO [1], OLEX2 [2], SHELX [3,4]
Table 2:

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

Atom x y z U iso*/U eq
Cu1 0.000000 0.01438 (6) 0.250000 0.0261 (3)
Cl1 0.13532 (5) −0.32244 (10) 0.27252 (16) 0.0388 (3)
O1 0.06290 (13) −0.1035 (3) 0.2386 (4) 0.0297 (7)
N1 0.04804 (16) 0.1346 (3) 0.1521 (4) 0.0293 (8)
C1 0.1442 (2) 0.0173 (4) 0.1451 (5) 0.0275 (9)
C2 0.11978 (19) −0.0901 (4) 0.1992 (5) 0.0274 (9)
C3 0.1624 (2) −0.1881 (4) 0.2091 (5) 0.0305 (10)
C4 0.2242 (2) −0.1796 (4) 0.1709 (6) 0.0347 (11)
H4 0.251430 −0.246814 0.181136 0.042*
C5 0.2461 (2) −0.0744 (5) 0.1184 (6) 0.0394 (12)
H5 0.288190 −0.069007 0.091237 0.047*
C6 0.2068 (2) 0.0227 (5) 0.1055 (6) 0.0368 (11)
H6 0.222149 0.095143 0.069167 0.044*
C7 0.1052 (2) 0.1211 (4) 0.1174 (5) 0.0293 (9)
H7 0.123246 0.186522 0.068779 0.035*
C8 0.0122 (2) 0.2433 (4) 0.0982 (5) 0.0280 (9)
H8A −0.030023 0.222788 0.026076 0.034*
H8B 0.036864 0.290208 0.027509 0.034*
C9 0.000000 0.3188 (6) 0.250000 0.0314 (14)
C10 −0.0596 (3) 0.3944 (5) 0.1857 (7) 0.0518 (14)
H10A −0.052208 0.441473 0.088005 0.078*
H10B −0.067401 0.446689 0.277602 0.078*
H10C −0.097360 0.343683 0.150312 0.078*

Source of material

The structure was solved with the OLEX2 program [2] as an interface together with the SHELXT and SHELXL programs [3, 4]. All H atoms were placed in geometrically idealized positions and refined using a riding model, with C–H = 0.98 (methylene), 0.95 Å (benzene), and with U iso(H) = 1.2 U eq(C) for H atoms.

Experimental details

3,5-Dibromosalicylaldehyde (0.0279 g, 0.10 mmol) was dissolved in methanol (30 ml) with stirring and 1,3-diaminopentane (0.05 mmol) was added. The mixture was stirred and refluxed at 80 °C for 3 h. The solvent was removed by a rotary evaporator to give a yellow powder which was dissolved in a mixture containing 20 mL methanol and 10 mL ethanol. Then, 0.1 g copper nitrate was added to the above solution and the resulting dark green mixture was further stirred at room temperature overnight. Dark greenish crystals of the title compound were isolated after two weeks.

Comment

Schiff base is a excellent ligand for 3d and 4f metal ion owing to its characteristic –C=N– group, in which the N atom has a lone pair of electrons, creating an electron-rich chemical environment [5, 6]. Meanwhile, the introduction of electron-rich atoms such as O, N and S into the Schiff base can create more favorable electron-rich chemical environment for coordination. As a part of our current research interest on the exploration of the regulating effect of Schiff base complexes [7, 8], we report herein a new complex based.

The asymmetric unit of the title structure contains one half of Cu(II) complex. As is shown in Figure, the central Cu(II) exhibits a tetra-coordinated environment which is defined by N2O2. The bond lengths of Cu–O(N) are in the range of 1.898(3)–1.948(4) Å which is compared favorably with the corresponding values observed in salen-type Cu(II) analogous [9, 10].

The dihedral angle calculated between the planes of two benzene rings is 38.135(16)°. Owing to the presence of π–π interactions (the distance between Cg1⃛Cg1 i are 3.603(2)), where Cg1 is the centroids of the C1–C6 ring). Two neighboring complexes are further linked to each other to form a self-assembled supramolecular dimer.


Corresponding author: Qiong Wu, Department of Chemical Science and Technology, Kunming University, Yunnan, Kunming 65200, P. R. China, E-mail:

Funding source: Fund for Less Developed National Nature Science Foundation of China

Award Identifier / Grant number: 31760257, 21761017

Funding source: Joint Basic Research Program (partial) of Yunnan Provincial Undergraduate Universities

Award Identifier / Grant number: 2017FH001-002

Funding source: Program for Innovative Research Team (in Science and Technology) in Universities of Yunnan Province

Award Identifier / Grant number: IRTSTYN

Funding source: Recruitment Program of Yunnan Province Experts Provincial Young Talents

Award Identifier / Grant number: 2019HB098

Funding source: Ten-Thousand Talents Program of Yunnan Province

Award Identifier / Grant number: YNWR-QNBJ-2018-273

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: This work was supported by Fund for Less Developed National Nature Science Foundation of China (No. 31760257, 21761017) as well as the Joint Basic Research Program (partial) of Yunnan Provincial Undergraduate Universities (2017FH001-002), the Program for Innovative Research Team (in Science and Technology) in Universities of Yunnan Province (IRTSTYN), the Recruitment Program of Yunnan Province Experts Provincial Young Talents (2019HB098) and the Ten-Thousand Talents Program of Yunnan Province (YNWR-QNBJ-2018-273).

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

References

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Received: 2021-09-29
Accepted: 2021-11-05
Published Online: 2021-11-17
Published in Print: 2022-02-23

© 2021 Rui Duan et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution 4.0 International License.

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