Crystal structure of tetramethylammonium (2-(3-ethoxy-2-oxidobenzylidene)-1-(2-hydroxybenzoyl)hydrazin-1-ido-κ3N,N′,O)cobalt(III), C36H40N5O8Co

Zhang Cuihong; Ge Yuan; Huo Xiaoping; Yang Liguo; Li Xin; Miao Zongcheng

doi:10.1515/ncrs-2018-0497

Open Access Published by De Gruyter (O) February 14, 2019

Crystal structure of tetramethylammonium (2-(3-ethoxy-2-oxidobenzylidene)-1-(2-hydroxybenzoyl)hydrazin-1-ido-κ³N,N′,O)cobalt(III), C₃₆H₄₀N₅O₈Co

Zhang Cuihong , Ge Yuan , Huo Xiaoping , Yang Liguo , Li Xin and Miao Zongcheng

From the journal Zeitschrift für Kristallographie - New Crystal Structures

https://doi.org/10.1515/ncrs-2018-0497

Abstract

C₃₆H₄₀N₅O₈Co, monoclinic, P2₁/c (no. 14), a = 17.353(4) Å, b = 11.474(2) Å, c = 18.074(4) Å, β = 101.056(2)°, V = 3532.0(13) Å³, Z = 4, R_gt(F) = 0.0464, wR_ref(F²) = 0.1323, T = 296(2) K 1–3.

CCDC no.: 1892526

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

Table 1:

Data collection and handling.

Crystal:	Red block
Size:	0.10 × 0.08 × 0.06 mm
Wavelength:	Mo Kα radiation (0.71073 Å)
μ:	0.54 mm⁻¹
Diffractometer, scan mode:	Bruker APEX-II CCD, φ and ω
θ_max, completeness:	26.5°, >99%
N(hkl)_measured, N(hkl)_unique, R_int:	33219, 7286, 0.041
Criterion for I_obs, N(hkl)_gt:	I_obs > 2 σ(I_obs), 5421
N(param)_refined:	469
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
Co1	0.24045(2)	0.25721(3)	0.57882(2)	0.03228(12)
N1	0.27353(12)	0.48825(18)	0.61118(12)	0.0384(5)
O1	0.24994(14)	0.70445(19)	0.63845(14)	0.0668(6)
H1	0.2725	0.6413	0.6434	0.100*
C1	−0.02061(17)	0.0614(3)	0.75505(17)	0.0553(8)
H1A	−0.0584	0.0030	0.7510	0.066*
O2	0.00632(14)	0.0043(2)	0.63735(12)	0.0659(6)
H2	0.0329	0.0236	0.6065	0.099*
N2	0.30763(11)	0.37843(18)	0.62017(11)	0.0347(5)
C2	−0.00747(18)	0.1320(3)	0.81745(18)	0.0615(8)
H2A	−0.0368	0.1215	0.8550	0.074*
O3	0.18907(10)	0.24943(14)	0.66318(9)	0.0368(4)
N3	0.11436(12)	0.11507(18)	0.58660(11)	0.0369(5)
C3	0.0489(2)	0.2184(3)	0.82504(19)	0.0659(9)
H3	0.0572	0.2666	0.8672	0.079*
O4	0.17116(10)	0.38264(14)	0.54242(9)	0.0373(4)
N4	0.16744(11)	0.14182(17)	0.54015(11)	0.0335(4)
C4	0.09257(18)	0.2325(3)	0.76988(17)	0.0510(7)
H4	0.1308	0.2903	0.7754	0.061*
C5	0.08082(14)	0.1619(2)	0.70552(14)	0.0362(5)
N5	0.23963(17)	0.9136(3)	0.82449(16)	0.0680(8)
O5	0.30993(10)	0.13781(16)	0.61862(10)	0.0432(4)
C6	0.02189(16)	0.0762(2)	0.69779(15)	0.0432(6)
O6	0.28588(11)	0.26709(16)	0.49345(10)	0.0442(4)
C7	0.13130(14)	0.1775(2)	0.64891(13)	0.0335(5)
O7	0.40203(14)	−0.0588(2)	0.63875(15)	0.0720(7)
O8	0.36805(16)	0.2996(2)	0.38529(16)	0.0802(8)
C8	0.16446(16)	0.0828(2)	0.47908(14)	0.0400(6)
H8	0.1265	0.0248	0.4678	0.048*
C9	0.21680(16)	0.1019(2)	0.42756(13)	0.0427(6)
C10	0.20912(19)	0.0264(3)	0.36479(15)	0.0545(8)
H10	0.1732	−0.0346	0.3599	0.065*
C13	0.31704(19)	0.2068(3)	0.37957(16)	0.0559(8)
C12	0.3072(2)	0.1335(4)	0.31849(17)	0.0674(10)
H12	0.3368	0.1452	0.2813	0.081*
C11	0.2539(2)	0.0421(4)	0.31121(17)	0.0694(10)
H11	0.2487	−0.0080	0.2701	0.083*
C14	0.27247(16)	0.1933(2)	0.43720(14)	0.0422(6)
C15^a	0.4388(4)	0.2880(7)	0.4152(8)	0.194(7)
H15A^a	0.4577	0.2187	0.3936	0.233*
H15B^a	0.4407	0.2715	0.4682	0.233*
C15′^b	0.4200(9)	0.2908(18)	0.3388(8)	0.106(15)
H15C^b	0.4035	0.3299	0.2908	0.127*
H15D^b	0.4365	0.2115	0.3317	0.127*
C36	0.2924(5)	0.8335(8)	0.8706(5)	0.224(4)
H36A	0.3146	0.7815	0.8388	0.336*
H36B	0.2639	0.7893	0.9017	0.336*
H36C	0.3336	0.8764	0.9020	0.336*
C35	0.1679(4)	0.8486(6)	0.7889(4)	0.151(2)
H35A	0.1330	0.9000	0.7565	0.227*
H35B	0.1421	0.8189	0.8274	0.227*
H35C	0.1823	0.7850	0.7599	0.227*
C34	0.2750(3)	0.9649(5)	0.7641(3)	0.1205(18)
H34A	0.2375	1.0151	0.7336	0.181*
H34B	0.2899	0.9038	0.7334	0.181*
H34C	0.3206	1.0092	0.7860	0.181*
C33	0.2132(4)	1.0072(4)	0.8684(3)	0.136(2)
H33A	0.2579	1.0438	0.8992	0.204*
H33B	0.1799	0.9755	0.9001	0.204*
H33C	0.1845	1.0638	0.8349	0.204*
C16	0.4953(3)	0.3799(6)	0.4114(4)	0.150(2)
H16A	0.5279	0.3584	0.3763	0.225*
H16B	0.5274	0.3913	0.4604	0.225*
H16C	0.4680	0.4509	0.3950	0.225*
C17	0.3987(3)	−0.0599(5)	0.5066(3)	0.1246(19)
H17A	0.4051	0.0229	0.5028	0.187*
H17B	0.3702	−0.0895	0.4596	0.187*
H17C	0.4494	−0.0964	0.5182	0.187*
C19	0.43366(18)	0.0516(3)	0.65431(17)	0.0557(8)
C18	0.3573(3)	−0.0840(4)	0.5636(3)	0.0901(13)
H18A	0.3425	−0.1656	0.5609	0.108*
H18B	0.3094	−0.0382	0.5552	0.108*
C20	0.38539(15)	0.1525(3)	0.64365(14)	0.0443(6)
C21	0.42262(16)	0.2617(3)	0.66253(16)	0.0467(7)
C22	0.50355(18)	0.2662(3)	0.6952(2)	0.0662(9)
H22	0.5270	0.3378	0.7093	0.079*
C23	0.5476(2)	0.1672(4)	0.7064(2)	0.0804(11)
H23	0.6006	0.1710	0.7284	0.097*
C24	0.5125(2)	0.0599(4)	0.6845(2)	0.0723(10)
H24	0.5431	−0.0073	0.6904	0.087*
C25	0.38076(14)	0.3702(3)	0.65106(14)	0.0425(6)
H25	0.4080	0.4384	0.6668	0.051*
C26	0.20202(14)	0.4792(2)	0.56884(13)	0.0347(5)
C27	0.15713(15)	0.5884(2)	0.55158(14)	0.0384(6)
C28	0.18269(17)	0.6950(2)	0.58620(16)	0.0476(7)
C29	0.1373(2)	0.7942(3)	0.5679(2)	0.0628(9)
H29	0.1542	0.8651	0.5902	0.075*
C30	0.0673(2)	0.7885(3)	0.5170(2)	0.0626(9)
H30	0.0372	0.8555	0.5057	0.075*
C31	0.04119(18)	0.6846(3)	0.48248(18)	0.0574(8)
H31	−0.0059	0.6815	0.4479	0.069*
C32	0.08590(16)	0.5857(2)	0.49999(16)	0.0463(6)
H32	0.0683	0.5156	0.4770	0.056*

^aOccupancy: 0.834(13), ^bOccupancy: 0.166(13).

Source of material

3-ethoxy-2-oxidobenzylidene(2-hydroxybenzo)hydrazine was synthesized according to the reference [4], the other reagents were commercially available and used as purchased.

A mixture of 3-ethoxy-2-oxidobenzylidene(2-hydroxybenzo)hydrazine (299.3 mg, 0.3 mmol), CoCl₂ (129.8 mg, 0.1 mmol) and methanol (10 mL) was heated at 60 °C for 10 h, and then cooled to room temperature. The resulting light red block crystals of the title compound were obtained. The yield is ca. 26%. IR(KBr-pellet): 3212(s), 1514(s), 1511(s), 1411(s), 1401(s), 1310(s), 1210(s), 1113(s), 1101(s), 1010(s), 1000(s), 914(s), 817(s), 801(m), 731(m), 711(m), 600(m), 444(m) cm⁻¹.

Experimental details

Hydrogen atoms are added using the standard options of the SHELX [3] system (Table 2). The ethyl group of the ligand shows a disorder (C15, C16; Figure).

Comment

The aroylhydrazones and there reactions still attract much attention due to their coordination ability to metal ions and their biological activity. In particular, aroylhydrazones with a pyridinyl moiety present high sensitivity and selectivity to some metals and have therefore been applied as analytical reagents. Such compounds as cis-(dimethyl sulfoxide-κO)[N′-(3-ethoxy-2-oxidobenzylidene-κO)-2-hydroxybenzohydrazidato-κ²N′,O]-dioxidomolybdenum(VI) and 2-hydroxy-3-methoxybenzaldehyde(pyridine-2-carbonyl)hydrazone have been synthesized and characterized by X-ray diffraction [5], [6], [7], [8]. We now report a similar compound, whose structure was determined by X-ray diffraction.

The compound crystallizes in the monoclinic space group P2₁/c with four formula units in the unit cell. As shown in the Figure, one formula unit consists of one cation, two dianionic ligands and one Co atom. The formal Co(III) metal ion is in a slightly distorted octahedredral coordination environment, with two nitrogen atoms and four oxygen atoms from the ligands. The average bond length of Co—N is 1.873 Å, while the average bond length of Co—O is 1.892 Å. Bond lengths and angles in the cation and the organic ligands are all in the expected regions [9].

Funding source: National Natural Science Foundation of China

Award Identifier / Grant number: 51602007

Award Identifier / Grant number: 51673157

Funding source: Natural Science Basic Research Plan in Shaanxi Province of China

Award Identifier / Grant number: 2017JM5134

Award Identifier / Grant number: 2018JM5047

Funding source: Shaanxi Provincial Education Department

Award Identifier / Grant number: 18JK1206

Funding source: Science Research Foundation

Award Identifier / Grant number: XJ17B07

Funding source: National Students–Platform for Innovation and Entrepreneurship Training Program

Award Identifier / Grant number: 201812715003

Funding statement: This work was supported by the National Natural Science Foundation of China (Grant No. 51602007, Grant No. 51673157), the Natural Science Basic Research Plan in Shaanxi Province of China (Grant No. 2017JM5134, Grant No. 2018JM5047), Scientific Research Program Funded by Shaanxi Provincial Education Department (Grant No.18JK1206), the Science Research Foundation of Xijing University (Grant No. XJ17B07), the National Students–Platform for Innovation and Entrepreneurship Training Program (Grant No. 201812715003).

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Received: 2018-11-09

Accepted: 2019-01-22

Published Online: 2019-02-14

Published in Print: 2019-03-26

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