The crystal structure of bis(μ2-5-chloro-2-oxido-N-(1-oxidoethylidene)benzohydrazonato-κ5N,O,O′:N′,O′′)hexkis(pyridine-κ1N)trinickel(II) - pyridine (1/1), C63H57Cl2N13Ni3O6

Liguo Yang; Xin Wang; Dan Luo; Nana Liu; Dayong Tian

doi:10.1515/ncrs-2020-0600

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

The crystal structure of bis(μ₂-5-chloro-2-oxido-N-(1-oxidoethylidene)benzohydrazonato-κ⁵N,O,O′:N′,O′′)hexkis(pyridine-κ¹N)trinickel(II) - pyridine (1/1), C₆₃H₅₇Cl₂N₁₃Ni₃O₆

Liguo Yang , Xin Wang , Dan Luo , Nana Liu and Dayong Tian

From the journal Zeitschrift für Kristallographie - New Crystal Structures

https://doi.org/10.1515/ncrs-2020-0600

Abstract

C₆₃H₅₇Cl₂N₁₃Ni₃O₆, monoclinic, P21/c, a = 16.136(4) Å, b = 16.432(4) Å, c = 23.881(6) Å, β = 101.900(3)°, V = 6196(3) Å³, Z = 4, R_gt(F) = 0.0461, wR_ref(F²) = 0.1357, T = 298 K [1], [2], [3].

CCDC no.: 2054630

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:	Red block
Size:	0.06 × 0.04 × 0.02 mm
Wavelength:	Mo Kα radiation (0.71073 Å)
μ:	1.05 mm⁻¹
Diffractometer, scan mode:	Bruker APEX-II, φ and ω
θ_max, completeness:	25.0°, >99%
N(hkl)_measured, N(hkl)_unique, R_int:	72,238, 10,897, 0.053
Criterion for I_obs, N(hkl)_gt:	I_obs > 2 σ(I_obs), 8298
N(param)_refined:	786
Programs:	Bruker [1], SHELX [2], [, 3]

Table 2:

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

Atom	x	y	z	U_iso*/U_eq
Ni1	0.30718 (2)	0.39503 (3)	0.28225 (2)	0.03055 (12)
Ni2	0.59164 (3)	0.40468 (3)	0.39023 (2)	0.03796 (14)
Ni3	0.02977 (3)	0.33339 (3)	0.17469 (2)	0.03905 (14)
O1	−0.03985 (14)	0.30837 (16)	0.23295 (11)	0.0453 (6)
O2	0.11658 (16)	0.36264 (18)	0.12628 (10)	0.0520 (7)
O3	0.21115 (14)	0.37930 (15)	0.32435 (10)	0.0393 (6)
O4	0.40322 (13)	0.41154 (15)	0.24046 (9)	0.0360 (5)
O5	0.50154 (14)	0.39447 (15)	0.43821 (10)	0.0406 (6)
O6	0.66494 (14)	0.41634 (17)	0.33259 (11)	0.0466 (6)
N1	−0.07082 (19)	0.3139 (2)	0.10421 (14)	0.0486 (8)
N2	−0.0134 (2)	0.4601 (2)	0.17227 (16)	0.0583 (10)
N3	0.0633 (2)	0.2044 (2)	0.16906 (15)	0.0516 (8)
N4	0.13045 (16)	0.35747 (17)	0.23514 (12)	0.0334 (6)
N5	0.20385 (16)	0.37956 (17)	0.21484 (12)	0.0344 (6)
N6	0.28788 (18)	0.52543 (17)	0.28177 (12)	0.0387 (7)
N7	0.33262 (19)	0.26500 (18)	0.28403 (13)	0.0413 (7)
N8	0.41164 (16)	0.40238 (17)	0.35037 (11)	0.0326 (6)
N9	0.48748 (16)	0.40517 (17)	0.32985 (12)	0.0338 (6)
N10	0.6033 (2)	0.2706 (2)	0.38994 (13)	0.0510 (8)
N11	0.69262 (19)	0.40791 (19)	0.46179 (14)	0.0462 (8)
N12	0.58868 (19)	0.5387 (2)	0.39976 (13)	0.0458 (8)
N14	0.7383 (9)	0.9771 (6)	0.5261 (4)	0.172 (4)
Cl1	0.57028 (8)	0.38651 (9)	0.08203 (5)	0.0736 (4)
Cl2	0.04575 (9)	0.34987 (11)	0.48288 (5)	0.0868 (4)
C1	0.7353 (4)	0.4230 (4)	0.5622 (2)	0.0870 (17)
H1	0.7207	0.4226	0.5979	0.104*
C2	0.8150 (4)	0.4379 (4)	0.5575 (3)	0.098 (2)
H2	0.8563	0.4496	0.5899	0.118*
C3	0.8353 (3)	0.4355 (4)	0.5046 (3)	0.101 (2)
H3	0.8907	0.4443	0.5004	0.122*
C4	0.7715 (3)	0.4198 (3)	0.4575 (2)	0.0710 (14)
H4	0.7850	0.4176	0.4215	0.085*
C5	0.6755 (3)	0.4085 (3)	0.51376 (18)	0.0643 (12)
H5	0.6201	0.3986	0.5174	0.077*
C6	0.6535 (4)	0.5834 (3)	0.3923 (3)	0.097 (2)
H6	0.6998	0.5567	0.3832	0.116*
C7	0.6572 (4)	0.6663 (4)	0.3971 (4)	0.118 (3)
H7	0.7054	0.6944	0.3923	0.142*
C8	0.5890 (4)	0.7075 (3)	0.4090 (2)	0.0741 (14)
H8	0.5878	0.7641	0.4103	0.089*
C9	0.5239 (3)	0.6622 (3)	0.4186 (2)	0.0715 (14)
H9	0.4771	0.6873	0.4282	0.086*
C10	0.5265 (3)	0.5789 (3)	0.4141 (2)	0.0612 (12)
H10	0.4809	0.5493	0.4217	0.073*
C11	0.6387 (2)	0.4115 (2)	0.27738 (15)	0.0368 (8)
C12	0.7005 (2)	0.4125 (2)	0.24263 (17)	0.0431 (9)
H12	0.7571	0.4181	0.2605	0.052*
C13	0.6807 (2)	0.4056 (2)	0.18399 (17)	0.0459 (9)
H13	0.7232	0.4068	0.1629	0.055*
C14	0.5969 (2)	0.3968 (2)	0.15679 (15)	0.0421 (9)
C15	0.5341 (2)	0.3977 (2)	0.18755 (15)	0.0379 (8)
H15	0.4780	0.3929	0.1683	0.045*
C16	0.5519 (2)	0.4055 (2)	0.24723 (14)	0.0326 (7)
C17	0.4765 (2)	0.40798 (19)	0.27399 (14)	0.0316 (7)
C18	0.4272 (2)	0.3947 (2)	0.40645 (14)	0.0341 (8)
C19	0.3542 (2)	0.3838 (3)	0.43533 (16)	0.0482 (10)
H19A	0.3551	0.3295	0.4504	0.072*
H19B	0.3022	0.3924	0.4082	0.072*
H19C	0.3585	0.4223	0.4660	0.072*
C20	0.5614 (3)	0.2236 (3)	0.4204 (2)	0.0700 (13)
H20	0.5267	0.2490	0.4417	0.084*
C21	0.5665 (4)	0.1400 (3)	0.4222 (3)	0.0897 (17)
H21	0.5367	0.1100	0.4446	0.108*
C22	0.6163 (5)	0.1021 (4)	0.3905 (3)	0.099 (2)
H22	0.6199	0.0456	0.3899	0.119*
C23	0.6608 (5)	0.1486 (4)	0.3595 (2)	0.102 (2)
H23	0.6962	0.1243	0.3382	0.122*
C24	0.6525 (4)	0.2325 (3)	0.3603 (2)	0.0794 (16)
H24	0.6829	0.2636	0.3390	0.095*
C25	0.3531 (3)	0.5769 (2)	0.29261 (18)	0.0513 (10)
H25	0.4076	0.5555	0.3002	0.062*
C26	0.3437 (3)	0.6602 (3)	0.2931 (2)	0.0628 (12)
H26	0.3908	0.6940	0.3013	0.075*
C27	0.2636 (3)	0.6920 (3)	0.2812 (2)	0.0688 (13)
H27	0.2554	0.7480	0.2804	0.083*
C28	0.1960 (3)	0.6401 (3)	0.2704 (2)	0.0679 (13)
H28	0.1410	0.6602	0.2629	0.081*
C29	0.2107 (2)	0.5574 (2)	0.27089 (18)	0.0508 (10)
H29	0.1644	0.5225	0.2632	0.061*
C30	0.3130 (3)	0.2185 (3)	0.3245 (2)	0.0643 (12)
H30	0.2784	0.2397	0.3476	0.077*
C31	0.3417 (4)	0.1395 (3)	0.3338 (2)	0.0885 (18)
H31	0.3275	0.1085	0.3630	0.106*
C32	0.3913 (4)	0.1077 (3)	0.2993 (3)	0.0870 (17)
H32	0.4099	0.0540	0.3038	0.104*
C33	0.4126 (4)	0.1549 (3)	0.2590 (3)	0.096 (2)
H33	0.4480	0.1353	0.2359	0.115*
C34	0.3816 (3)	0.2328 (3)	0.2523 (3)	0.0768 (15)
H34	0.3961	0.2647	0.2236	0.092*
C35	0.0100 (4)	0.1449 (3)	0.1628 (4)	0.128 (3)
H35	−0.0464	0.1573	0.1623	0.154*
C36	0.0304 (5)	0.0634 (4)	0.1565 (4)	0.148 (4)
H36	−0.0119	0.0240	0.1506	0.177*
C37	0.1084 (6)	0.0431 (4)	0.1591 (3)	0.125 (3)
H37	0.1223	−0.0089	0.1487	0.150*
C38	0.1715 (5)	0.1009 (4)	0.1779 (4)	0.117 (2)
H38	0.2284	0.0868	0.1890	0.140*
C39	0.1437 (4)	0.1809 (4)	0.1789 (4)	0.123 (3)
H39	0.1849	0.2213	0.1871	0.148*
C40	−0.1490 (2)	0.2981 (3)	0.1111 (2)	0.0599 (11)
H40	−0.1584	0.2933	0.1481	0.072*
C41	−0.2159 (3)	0.2888 (3)	0.0663 (3)	0.0801 (16)
H41	−0.2697	0.2776	0.0728	0.096*
C42	−0.2033 (4)	0.2960 (4)	0.0122 (3)	0.0891 (19)
H42	−0.2481	0.2903	−0.0190	0.107*
C43	−0.1228 (4)	0.3118 (4)	0.0043 (2)	0.099 (2)
H43	−0.1120	0.3165	−0.0323	0.118*
C44	−0.0589 (3)	0.3205 (3)	0.0515 (2)	0.0742 (14)
H44	−0.0046	0.3315	0.0461	0.089*
C45	0.0266 (4)	0.5210 (3)	0.1542 (3)	0.108 (2)
H45	0.0755	0.5104	0.1406	0.129*
C46	−0.0022 (6)	0.6024 (4)	0.1548 (4)	0.148 (4)
H46	0.0286	0.6445	0.1429	0.178*
C47	−0.0733 (7)	0.6182 (5)	0.1723 (4)	0.151 (5)
H47	−0.0931	0.6713	0.1721	0.181*
C48	−0.1167 (6)	0.5569 (4)	0.1905 (3)	0.117 (3)
H48	−0.1672	0.5665	0.2025	0.141*
C49	−0.0836 (4)	0.4796 (3)	0.1906 (2)	0.0814 (16)
H49	−0.1124	0.4377	0.2046	0.098*
C50	0.0205 (3)	0.3395 (3)	0.40822 (17)	0.0511 (10)
C51	−0.0608 (3)	0.3196 (2)	0.38023 (19)	0.0528 (10)
H51	−0.1033	0.3119	0.4008	0.063*
C52	−0.0779 (2)	0.3113 (2)	0.32200 (18)	0.0460 (9)
H52	−0.1331	0.2985	0.3038	0.055*
C53	−0.0167 (2)	0.3211 (2)	0.28761 (16)	0.0375 (8)
C54	0.0666 (2)	0.3437 (2)	0.31787 (15)	0.0347 (8)
C55	0.0827 (2)	0.3518 (2)	0.37748 (16)	0.0419 (9)
H55	0.1369	0.3658	0.3968	0.050*
C56	0.1409 (2)	0.3606 (2)	0.29093 (15)	0.0324 (7)
C57	0.1883 (2)	0.3806 (2)	0.15869 (15)	0.0406 (8)
C58	0.2588 (2)	0.4047 (3)	0.13024 (17)	0.0580 (12)
H58A	0.2693	0.3617	0.1055	0.087*
H58B	0.3090	0.4148	0.1588	0.087*
H58C	0.2432	0.4532	0.1082	0.087*
C59	0.6863 (8)	0.8488 (6)	0.5177 (4)	0.142 (4)
H59	0.6393	0.8148	0.5138	0.171*
C60	0.6740 (8)	0.9273 (7)	0.5182 (4)	0.151 (4)
H60	0.6192	0.9478	0.5129	0.182*
C61	0.7589 (9)	0.8161 (6)	0.5223 (4)	0.136 (3)
H61	0.7640	0.7597	0.5220	0.163*
C62	0.8171 (9)	0.9487 (8)	0.5301 (4)	0.151 (4)
H62	0.8636	0.9832	0.5343	0.181*
C63	0.8258 (8)	0.8616 (7)	0.5275 (3)	0.148 (4)
H63	0.8788	0.8382	0.5295	0.178*

Source of material

The educt N′-acetyl-5-chloro-2-hydroxybenzohydrazide (LH₃), intended to be the bridging ligand in its deprotonated form was synthesized according to reference [4]. A mixture of LH₃ (0.196 g, 1 mmol) and nickel acetate (0.162 g, 1 mmol) and a few drops of a NaOH solution in 10 ml methanol was stirred at room temperature for 1 h. The mixture was filtered to remove impurties, and then left at room temperature. After a few days, red blocks of the ligand were formed. Yield (0.23 g, 60%).

Experimental details

H atoms were geometrically placed (C—H = 0.95–0.98 Å) and refined as riding with U_iso(H) = 1.2–1.5 U_eq(C) [3].

Comment

Pentadentate ligands have been synthesized in recent years [5]. Pentadentate ligands can react with the transition metals and rare earth metals [6], [, 7]. A lot of the ring structure containing complexes and metallacrown complexes have been synthesized. In recent years, our group synthesized several pentadentate ligands, the ligand L/LH₃ is one of them. The new ligand reacts with the transition metals [8].

As shown in the Figure, the title compound crystallizes in the monoclinic space group P21/c with four formula units in the unit cell. The bond lengths of Ni–O are 2.030, 2.000, 2.035, 2.003 and 2.049 Å, the bond lengths of Ni–N are 2.081, 2.091, 2.165, 2.174, 1.976, 2.105, 2.211, 2.215, 1.978, 2.108, 2.193 and 2.198 Å, respectively, the bond lengths of Ni–N from the pyridine molecule is longer than the bond lengths of Ni–N from the anionic ligands, which are similar with the reference [8]. The trinuclear complex is almost centrosymmetric but this symmetry is not supported by the crystallographic findings. The Ni complex is formed by two chelated ligands three nickel ions and eight pyridine molecules. We can see that each nickel ion resides in a slightly distorted octahedral coordination environment, consisting of three pyridine N, a phenolate O, a carbonyl oxido O and an imine-type nitrogen of L, which construct the five-membered and six-membered rings with each nickel atom.

Corresponding author: Yang Liguo, College of Chemistry and Environmental Engineering, Anyang Institute of Technology, Anyang, 455000, Henan, P. R. China, E-mail: lgyang@ayit.edu.cn

Funding source: Natural Science Foundation of Henan Province of China

Award Identifier / Grant number: 202300410010

Funding source: Anyang Institute of Technoloty

Award Identifier / Grant number: YPY2019011

Award Identifier / Grant number: YPY2020025

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: Natural Science Foundation of Henan Province of China (Nos. 202300410010), Research Fund of Anyang Institute of Technology (Nos. YPY2019011, YPY2020025), Key discipline of environmental engineer of Anyang Institute of Technology.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2020-11-06

Accepted: 2021-01-08

Published Online: 2021-01-22

Published in Print: 2021-05-26

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