Crystal structure of bis{μ2-bis{(((((1-methoxyimino)ethyl)phenyl)imino)methyl)-2-phenolato-κ3N,O:O}copper(II)}, C68H68Cu2N8O8

Jing Huang; Jin-Xia Ma; Ping Wei; Ji-Xing Zhao

doi:10.1515/ncrs-2019-0062

Open Access Published by De Gruyter (O) May 8, 2019

Crystal structure of bis{μ₂-bis{(((((1-methoxyimino)ethyl)phenyl)imino)methyl)-2-phenolato-κ³N,O:O}copper(II)}, C₆₈H₆₈Cu₂N₈O₈

Jing Huang , Jin-Xia Ma , Ping Wei and Ji-Xing Zhao

From the journal Zeitschrift für Kristallographie - New Crystal Structures

https://doi.org/10.1515/ncrs-2019-0062

Abstract

C₆₈H₆₈Cu₂N₈O₈, monoclinic, P2₁/c, a = 16.241(3) Å, b = 12.1604(19) Å, c = 15.531(3) Å, β = 96.364(3)°, Z = 2, V = 3048.3(9) Å³, R_gt(F) = 0.0497, wR_ref(F²) = 0.1263, T = 296(2)K.

CCDC no.: 1906567

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:	Dark brown block
Size:	0.27 × 0.26 × 0.22 mm
Wavelength:	Mo Kα radiation (0.71073 Å)
μ:	0.76 mm⁻¹
Diffractometer, scan mode:	Bruker APEX-II, φ and ω-scans
θ_max, completeness:	27.6°, >99%
N(hkl)_measured, N(hkl)_unique, R_int:	20682, 7046, 0.061
Criterion for I_obs, N(hkl)_gt:	I_obs > 2 σ(I_obs), 4271
N(param)_refined:	392
Programs:	Bruker programs [1], SHELX [2], OLEX2 [3]

Table 2:

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

Atom	x	y	z	U_iso*/U_eq
Cu1	0.50267(2)	0.58933(3)	0.58334(3)	0.03836(13)
N1	0.44797(13)	0.71956(17)	0.51555(16)	0.0384(6)
N2	0.07705(19)	0.8166(3)	0.5883(3)	0.0961(13)
N3	0.57240(13)	0.48781(18)	0.66722(17)	0.0383(6)
N4	0.95590(16)	0.4472(3)	0.6188(2)	0.0697(9)
O1	0.57367(11)	0.56515(14)	0.49471(14)	0.0409(5)
O2	0.00108(16)	0.8596(3)	0.6081(3)	0.1143(13)
O3	0.43190(12)	0.61882(16)	0.66898(15)	0.0491(6)
O4	1.03612(15)	0.4091(2)	0.6061(2)	0.0849(9)
C1	0.60360(17)	0.6427(2)	0.4473(2)	0.0374(7)
C2	0.67952(18)	0.6268(2)	0.4140(2)	0.0491(8)
H2	0.709734	0.563249	0.428737	0.059*
C3	0.71048(19)	0.7021(3)	0.3604(2)	0.0563(9)
H3	0.760915	0.688749	0.339254	0.068*
C4	0.6676(2)	0.7979(3)	0.3373(2)	0.0595(10)
H4	0.688371	0.848643	0.300479	0.071*
C5	0.5943(2)	0.8163(2)	0.3698(2)	0.0525(9)
H5	0.565250	0.880479	0.354214	0.063*
C6	0.56080(17)	0.7424(2)	0.4258(2)	0.0390(7)
C7	0.48410(17)	0.7705(2)	0.4570(2)	0.0425(7)
H7	0.457126	0.832379	0.432589	0.051*
C8	0.37071(17)	0.7648(2)	0.5364(2)	0.0417(7)
C9	0.36063(18)	0.8760(2)	0.5518(2)	0.0477(8)
H9	0.404643	0.924257	0.548835	0.057*
C10	0.28483(19)	0.9151(2)	0.5715(2)	0.0540(9)
H10	0.279098	0.989699	0.582439	0.065*
C11	0.21759(19)	0.8467(3)	0.5755(2)	0.0525(9)
C12	0.22922(19)	0.7352(3)	0.5580(2)	0.0586(10)
H12	0.184701	0.687181	0.558600	0.070*
C13	0.30369(18)	0.6947(2)	0.5401(2)	0.0516(9)
H13	0.309651	0.619833	0.530264	0.062*
C14	0.1354(2)	0.8868(3)	0.5964(3)	0.0658(11)
C15	0.1242(3)	1.0016(3)	0.6272(3)	0.0998(16)
H15A	0.126060	1.051828	0.579741	0.150*
H15B	0.167777	1.019065	0.672048	0.150*
H15C	0.071639	1.007782	0.649596	0.150*
C16	−0.0622(3)	0.7776(4)	0.5916(5)	0.167(3)
H16A	−0.062811	0.750697	0.532728	0.201*
H16B	−0.050368	0.716126	0.630769	0.201*
C17	−0.1400(3)	0.8224(5)	0.6032(5)	0.182(4)
H17A	−0.144886	0.829370	0.664008	0.273*
H17B	−0.182932	0.774754	0.577155	0.273*
H17C	−0.145467	0.893514	0.576384	0.273*
C18	0.33830(19)	0.5704(3)	0.7675(2)	0.0497(8)
H18	0.304439	0.629353	0.748822	0.060*
C19	0.3157(2)	0.5038(3)	0.8322(2)	0.0578(9)
H19	0.267507	0.519038	0.857078	0.069*
C20	0.3638(2)	0.4137(3)	0.8611(3)	0.0632(10)
H20	0.347821	0.368299	0.904491	0.076*
C21	0.4353(2)	0.3932(3)	0.8245(2)	0.0541(9)
H21	0.467694	0.333079	0.843671	0.065*
C22	0.46104(17)	0.4604(2)	0.7589(2)	0.0410(7)
C23	0.41170(17)	0.5518(2)	0.7287(2)	0.0404(7)
C24	0.53952(17)	0.4397(2)	0.7298(2)	0.0424(8)
H24	0.571236	0.384940	0.759136	0.051*
C25	0.65633(17)	0.4564(2)	0.6575(2)	0.0423(7)
C26	0.68336(18)	0.3500(2)	0.6717(2)	0.0497(8)
H26	0.646361	0.296424	0.686094	0.060*
C27	0.76483(18)	0.3216(3)	0.6648(2)	0.0565(9)
H27	0.781884	0.249368	0.675173	0.068*
C28	0.82126(18)	0.3985(3)	0.6427(2)	0.0513(8)
C29	0.79328(18)	0.5062(3)	0.6282(2)	0.0546(9)
H29	0.830210	0.559697	0.613516	0.066*
C30	0.71214(18)	0.5352(2)	0.6351(2)	0.0486(8)
H30	0.694841	0.607414	0.624875	0.058*
C31	0.9087(2)	0.3672(3)	0.6327(3)	0.0608(10)
C32	0.9354(2)	0.2501(3)	0.6379(4)	0.1046(18)
H32A	0.994038	0.245849	0.634987	0.157*
H32B	0.906886	0.209848	0.590383	0.157*
H32C	0.922447	0.218946	0.691569	0.157*
C33	1.0885(2)	0.5029(4)	0.6069(3)	0.0847(14)
H33A	1.060748	0.560113	0.571086	0.102*
H33B	1.138918	0.483465	0.582446	0.102*
C34	1.1097(3)	0.5453(5)	0.6953(4)	0.127(2)
H34A	1.059877	0.564256	0.719844	0.191*
H34B	1.143955	0.609420	0.693492	0.191*
H34C	1.139184	0.489854	0.730353	0.191*

Source of material

Synthesis of the ligand: All solvents and other reagents were of analytical grade and the ligand was prepared by modification of the reported method [4], [5], [6]. To an ethanolic solution (8 mL) of 1-(4-aminophenyl)ethan-1-one O-ethyl oxime (328.0 mg, 2 mmol) was added an ethanolic solution (5 mL) of salicylaldehyde (244.1 mg, 2 mmol). After stirring and refluxing for 9 hours at 328 K, the mixture was filtered at room temperature. The product was dried under vacuum and a yellow solid was obtained (yield 67.3%, m.p. 389–397 K). Elemental analysis: Anal. Calcd. For C₁₇H₁₈N₂O₂: C, 72.32%; H, 6.43%; N, 9.92%; Found: C, 72.61%; H, 6.71%; N, 9.71%.

Synthesis of the copper(II) complex: To an ethanolic solution (2 mL) of copper(II) acetate monohydrate (2.0 mg, 10 mmol) was added an chloroform solution (4 mL) of ligand (5.7 mg, 20 mmol) at room temperature. The mixture was filtered after being stirred for 2 h. Then the filtrate was allowed to stand for 12 days. Several clear dark brown crystals were obtained. Anal. Calcd. for C₆₈H₆₈Cu₂N₈O₈: C, 65.21%; H, 5.47%; N, 8.95%. Found: C, 65.45%; H, 5.76%; N, 8.72%.

Experimental details

Hydrogen atoms were placed in their geometrically idealized positions and constrained to ride on their parent atoms.

Comment

Schiff bases have been reported as an important class of ligands [7]. Their metal complexes have been widely studied [8], [9], [10], [11]. Our research group has focus on the study of Schiff base and their complexes. Recently much attention is being focused on analytical reagents for the detection and determination of some metal ions [12], [13], specific properties [14], [15] and supramolecular architectures [16], [17], [18] etc.

The single crystal structure of the title complex was determined by X-ray crystallography. This crystal structure of the title complex is built up by the C₆₈H₆₈Cu₂N₈O₈ complex (cf. the figure). In the title complex, Cu1 atom is five-coordinate, with a N₂O₃ coordination environment with three O atoms (O1, O3 and O1ⁱ) and two N atoms (N1 and N3). The Cu1—O1 bond length is 1.914(2) Å and the Cu1—O3 is 1.886(2) Å and Cu1—O1ⁱ is 2.490 Å, respectively. The Cu1—N1 bond length is 2.049(2) Å and the Cu1—N3 is 2.044(2) Å, respectively.

Geometric parameters are all in the expected ranges for such a complex.

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Received: 2019-01-20

Accepted: 2019-03-29

Published Online: 2019-05-08

Published in Print: 2019-06-26

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