The crystal structure of bis(6-phenylpyridine-2-carboxylato-κ2
N,O)copper(II), C24H16N2O4Cu

Wang Li-Hua; Liang Lei; Li Xiang-Tao; Cao Shu-Hua; Tai Xi-Shi

doi:10.1515/ncrs-2021-0293

Open Access Published by De Gruyter (O) September 22, 2021

The crystal structure of bis(6-phenylpyridine-2-carboxylato-κ² N,O)copper(II), C₂₄H₁₆N₂O₄Cu

Wang Li-Hua , Liang Lei , Li Xiang-Tao , Cao Shu-Hua and Tai Xi-Shi

From the journal Zeitschrift für Kristallographie - New Crystal Structures

https://doi.org/10.1515/ncrs-2021-0293

Abstract

C₂₄H₁₆N₂O₄Cu, triclinic, P 1 ‾ (no. 2), a = 11.2454(6) Å, b = 13.5960(7) Å, c = 14.0076(8) Å, V = 1958.9(2) Å³, α = 79.019(5)°, β = 71.729(5)°, γ = 76.126(5)°, Z = 4, R _gt(F) = 0.0438, wR _ref(F ²) = 0.1030, T = 150 K.

CCDC no.: 2108727

One of the two crystallographically independent Cu(II) complexes 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:	Green block
Size:	0.12 × 0.11 × 0.10 mm
Wavelength:	Mo Kα radiation (0.71073 Å)
μ:	1.15 mm⁻¹
Diffractometer, scan mode:	SuperNova, ω
θ _max, completeness:	25.0°, 99%
N(hkl)_measured, N(hkl)_unique, R _int:	12,959, 6850, 0.037
Criterion for I _obs, N(hkl)_gt:	I _obs > 2 σ(I _obs), 5525
N(param)_refined:	559
Programs:	Bruker [1], Olex2 [2], SHELX [3], Diamond [4]

Table 2:

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

Atom	x	y	z	U _iso*/U _eq
Cu1	0.47135 (4)	0.36703 (3)	−0.00940 (3)	0.01507 (12)
O1	0.8121 (2)	0.38318 (17)	−0.00452 (18)	0.0234 (6)
O2	0.6290 (2)	0.41365 (17)	−0.04643 (17)	0.0198 (5)
O3	0.4163 (2)	0.43253 (17)	−0.12634 (16)	0.0183 (5)
O4	0.2494 (2)	0.4538 (2)	−0.18717 (18)	0.0298 (6)
N1	0.5682 (2)	0.24241 (19)	0.05580 (19)	0.0140 (6)
N2	0.2892 (2)	0.36682 (19)	0.05673 (19)	0.0134 (6)
C1	0.5310 (3)	0.1537 (2)	0.1029 (2)	0.0176 (7)
C2	0.5941 (3)	0.0918 (3)	0.1708 (3)	0.0236 (8)
H2	0.565617	0.033002	0.207054	0.028*
C3	0.6980 (4)	0.1174 (3)	0.1840 (3)	0.0249 (8)
H3	0.738621	0.077277	0.230657	0.030*
C4	0.7423 (3)	0.2033 (3)	0.1278 (2)	0.0189 (8)
H4	0.816359	0.218867	0.132232	0.023*
C5	0.6743 (3)	0.2651 (2)	0.0650 (2)	0.0144 (7)
C6	0.7116 (3)	0.3618 (2)	0.0008 (2)	0.0162 (7)
C7	0.4264 (3)	0.1268 (2)	0.0767 (3)	0.0174 (7)
C8	0.3309 (3)	0.0833 (3)	0.1505 (3)	0.0247 (8)
H8	0.336002	0.066381	0.216851	0.030*
C9	0.2291 (4)	0.0650 (3)	0.1260 (3)	0.0307 (9)
H9	0.164233	0.038210	0.176016	0.037*
C10	0.2241 (4)	0.0870 (3)	0.0265 (3)	0.0355 (10)
H10	0.155572	0.074778	0.009917	0.043*
C11	0.3197 (4)	0.1267 (3)	−0.0482 (3)	0.0274 (9)
H11	0.316553	0.139810	−0.115079	0.033*
C12	0.4203 (3)	0.1470 (3)	−0.0233 (3)	0.0209 (8)
H12	0.484474	0.174284	−0.073585	0.025*
C13	0.2995 (3)	0.4290 (2)	−0.1177 (3)	0.0193 (8)
C14	0.2240 (3)	0.3922 (2)	−0.0132 (2)	0.0158 (7)
C15	0.0965 (3)	0.3869 (2)	0.0119 (3)	0.0197 (8)
H15	0.053908	0.400949	−0.037827	0.024*
C16	0.0334 (3)	0.3603 (3)	0.1119 (3)	0.0259 (9)
H16	−0.052350	0.355959	0.130661	0.031*
C17	0.0993 (3)	0.3405 (3)	0.1832 (3)	0.0222 (8)
H17	0.056855	0.325009	0.251158	0.027*
C18	0.2283 (3)	0.3432 (2)	0.1553 (2)	0.0166 (7)
C19	0.3021 (3)	0.3258 (2)	0.2304 (2)	0.0163 (7)
C20	0.2830 (3)	0.2501 (3)	0.3139 (2)	0.0216 (8)
H20	0.221951	0.210798	0.323719	0.026*
C21	0.3546 (3)	0.2334 (3)	0.3819 (3)	0.0272 (9)
H21	0.343072	0.181918	0.436272	0.033*
C22	0.4434 (3)	0.2934 (3)	0.3690 (3)	0.0283 (9)
H22	0.491755	0.282182	0.414472	0.034*
C23	0.4601 (3)	0.3703 (3)	0.2880 (3)	0.0221 (8)
H23	0.519048	0.411157	0.279836	0.026*
C24	0.3898 (3)	0.3866 (3)	0.2196 (2)	0.0176 (7)
H24	0.401320	0.438634	0.165839	0.021*
Cu2	1.00839 (4)	0.13203 (3)	−0.47829 (3)	0.01778 (12)
O5	0.9162 (2)	0.11547 (18)	−0.72097 (17)	0.0250 (6)
O6	1.0172 (2)	0.08432 (18)	−0.60066 (17)	0.0220 (6)
O7	1.1771 (2)	0.07280 (17)	−0.46650 (16)	0.0192 (5)
O8	1.2948 (2)	0.0688 (2)	−0.36298 (19)	0.0321 (6)
N3	0.9029 (2)	0.2582 (2)	−0.53186 (19)	0.0151 (6)
N4	0.9638 (3)	0.1379 (2)	−0.3318 (2)	0.0168 (6)
C25	0.8637 (3)	0.2375 (3)	−0.6061 (2)	0.0186 (8)
C26	0.9351 (3)	0.1376 (3)	−0.6471 (2)	0.0199 (8)
C27	0.7712 (3)	0.3043 (3)	−0.6439 (3)	0.0233 (8)
H27	0.745555	0.288584	−0.695283	0.028*
C28	0.7174 (4)	0.3956 (3)	−0.6033 (3)	0.0283 (9)
H28	0.652838	0.441333	−0.625788	0.034*
C29	0.7603 (3)	0.4182 (3)	−0.5294 (3)	0.0242 (8)
H29	0.724771	0.479233	−0.501804	0.029*
C30	0.8567 (3)	0.3495 (3)	−0.4962 (2)	0.0187 (8)
C31	0.9184 (3)	0.3733 (2)	−0.4269 (2)	0.0184 (8)
C32	1.0510 (3)	0.3503 (3)	−0.4491 (3)	0.0226 (8)
H32	1.099580	0.322956	−0.508520	0.027*
C33	1.1108 (4)	0.3680 (3)	−0.3831 (3)	0.0287 (9)
H33	1.199345	0.352157	−0.398076	0.034*
C34	1.0390 (4)	0.4094 (3)	−0.2945 (3)	0.0343 (10)
H34	1.079088	0.420635	−0.249784	0.041*
C35	0.9079 (4)	0.4339 (3)	−0.2732 (3)	0.0302 (9)
H35	0.859501	0.461271	−0.213801	0.036*
C36	0.8481 (3)	0.4178 (2)	−0.3397 (3)	0.0238 (8)
H36	0.759896	0.437046	−0.325909	0.029*
C37	1.1925 (3)	0.0842 (3)	−0.3819 (3)	0.0208 (8)
C38	1.0703 (3)	0.1178 (2)	−0.3015 (3)	0.0183 (7)
C39	1.0671 (4)	0.1298 (3)	−0.2052 (3)	0.0247 (8)
H39	1.141907	0.117809	−0.186041	0.030*
C40	0.9499 (4)	0.1601 (3)	−0.1378 (3)	0.0320 (10)
H40	0.944929	0.169499	−0.072553	0.038*
C41	0.8409 (4)	0.1761 (3)	−0.1674 (3)	0.0264 (9)
H41	0.761823	0.194825	−0.121485	0.032*
C42	0.8480 (3)	0.1647 (2)	−0.2657 (2)	0.0190 (8)
C43	0.7331 (3)	0.1776 (2)	−0.3004 (2)	0.0186 (7)
C44	0.6271 (3)	0.2538 (3)	−0.2698 (3)	0.0243 (8)
H44	0.628896	0.298754	−0.228092	0.029*
C45	0.5194 (3)	0.2635 (3)	−0.3006 (3)	0.0287 (9)
H45	0.449866	0.315749	−0.281008	0.034*
C46	0.5146 (4)	0.1952 (3)	−0.3609 (3)	0.0307 (9)
H46	0.441200	0.200751	−0.380364	0.037*
C47	0.6193 (3)	0.1189 (3)	−0.3921 (3)	0.0274 (9)
H47	0.616644	0.074029	−0.433531	0.033*
C48	0.7275 (3)	0.1094 (3)	−0.3619 (2)	0.0222 (8)
H48	0.797163	0.057487	−0.382312	0.027*

Source of material

About 0.5 mmol (0.0996 g) of 6-phenylpyridine-2-carboxylic acid, 0.5 mmol (0.020 g) of NaOH and 0.25 mmol of (0.0499 g) copper(II) acetate monohydrate were added to 20 ml of water-ethanol (v:v = 1:1) at room temperature. After 10 min, precipitation appeared in the solution. The mixture was continuously stirred for 4.5 h at 85 °C. The solution was cooled to room temperature and filtered. After 16 days, the green crystals of the title compound were obtained from the filtrate.

Experimental details

The hydrogen atoms were positioned geometrically (C–H = 0.93 Å). Their U _iso values were set to 1.2U _eq of the parent atoms.

Comment

Some copper complexes with ligands containing a pyridine-carboxylate moiety exhibit novel coordination compounds [5] and excellent properties in many ways such as non-linear optical (NLO) property, antitumor activity, electrical conductance property, magnetic property [6], [7], [8], [9]. Therefore, studies on structure and property of copper complexes have been one of the hot topics. In our previous work, some metal complexes with ligands containing pyridine-carboxylate moieties have been synthesized and structural characterized [10], [11], [12]. In order to further enrich the structure of the copper complexes with ligands such, a new Cu(II) complex was synthesized using 6-phenylpyridine-2-carboxylic acid, NaOH and cupric acetate monohydrate as raw materials.

The asymmetric unit of Cu(II) complex contains two Cu(II) ion and four bidentate 6-phenylpyridine-2-carboxylate ligands. Each Cu(II) ion is four-coordinated with two O atoms and two N atoms from two different 6-phenylpyridine-2-carboxylate ligands. The sum of bond angles around Cu1, for example is 372.47°, showing that the O2, N1, N2, O3 is almost coplanar. The complex molecules form a 1D chained structure by the π-π stacking of phenyl and pyridine rings.

Corresponding author: Tai Xi-Shi, College of Chemistry and Chemical Engineering, Weifang University, Weifang, Shandong 261061, P. R. China, E-mail: taixs@wfu.edu.cn

Funding source: National Natural Science Foundation of China http://dx.doi.org/10.13039/501100001809

Award Identifier / Grant number: 21171132

Funding source: Natural Science Foundation of Shandong http://dx.doi.org/10.13039/501100007129

Award Identifier / Grant number: ZR2014BL003

Funding source: Project of Shandong Province Higher Educational Science and Technology Program http://dx.doi.org/10.13039/501100015642

Award Identifier / Grant number: J14LC01

Funding source: Science Foundation of Weifang

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: This project was supported by the National Natural Science Foundation of China (No. 21171132, http://dx.doi.org/10.13039/501100001809), the Natural Science Foundation of Shandong (ZR2014BL003, http://dx.doi.org/10.13039/501100007129), the Project of Shandong Province Higher Educational Science and Technology Program (J14LC01, http://dx.doi.org/10.13039/501100015642) and Science Foundation of Weifang.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2021-07-08

Accepted: 2021-09-09

Published Online: 2021-09-22

Published in Print: 2021-12-20

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

The crystal structure of bis(6-phenylpyridine-2-carboxylato-κ² N,O)copper(II), C₂₄H₁₆N₂O₄Cu

Abstract

Source of material

Experimental details

Comment

References

Journal and Issue

Articles in the same Issue

The crystal structure of bis(6-phenylpyridine-2-carboxylato-κ2 N,O)copper(II), C24H16N2O4Cu

Abstract

Source of material

Experimental details

Comment

References

Journal and Issue

Articles in the same Issue

The crystal structure of bis(6-phenylpyridine-2-carboxylato-κ² N,O)copper(II), C₂₄H₁₆N₂O₄Cu