Crystal structure of bis(3,3-dimethyl-1-phenylbut-1-en-2-yl)(trimethylsilyl)amido-k1N)zinc(II), Zn(C15H24NSi)2

Jun-Hong Wang; Hong-Bo Tong; Meng-Liang Wang; Hai-Yan Yuan

doi:10.1515/ncrs-2021-0057

Open Access Published by De Gruyter (O) March 15, 2021

Crystal structure of bis(3,3-dimethyl-1-phenylbut-1-en-2-yl)(trimethylsilyl)amido-k¹N)zinc(II), Zn(C₁₅H₂₄NSi)₂

Jun-Hong Wang , Hong-Bo Tong , Meng-Liang Wang and Hai-Yan Yuan

From the journal Zeitschrift für Kristallographie - New Crystal Structures

https://doi.org/10.1515/ncrs-2021-0057

Abstract

Zn(C₁₅H₂₄NSi)₂, triclinic, P1‾ (no. 2), a = 8.828(3) Å, b = 9.458(3) Å, c = 10.786(3) Å, α = 74.609(4)°, β = 73.915(4)°, γ = 64.888(4)°, V = 772.1(4) Å³, Z = 1, R_gt(F) = 0.0476, wR_ref(F²) = 0.1225, T = 293 K.

CCDC no.: 2065271

The molecular structure is shown in the figure (′ = −x, 2−y, 1−z). 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:	Colorless block
Size:	0.60 × 0.40 × 0.30 mm
Wavelength:	Mo Kα radiation (0.71073 Å)
μ:	0.89 mm⁻¹
Diffractometer, scan mode:	SMART, φ and ω
θ_max, completeness:	25.0°, 97 %
N(hkl)_measured, N(hkl)_unique, R_int:	3179, 2659, 0.022
Criterion for I_obs, N(hkl)_gt:	I > 2σ(I), 2158
N(param)_refined:	166
Programs:	Bruker [1], SHELX [2], [3], Olex2 [4]

Table 2:

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

Atom	x	y	z	U_iso*/U_eq
Zn	0.000000	1.000000	0.500000	0.0339 (2)
N	0.1660 (3)	0.9424 (3)	0.3550 (2)	0.0296 (5)
Si	0.27684 (10)	1.06528 (9)	0.28675 (8)	0.0334 (2)
C1	0.1988 (4)	0.7902 (3)	0.3315 (3)	0.0298 (6)
C2	0.2465 (4)	0.6594 (3)	0.4208 (3)	0.0356 (7)
H2	0.264847	0.566341	0.394734	0.043*
C3	0.2748 (4)	0.6390 (3)	0.5540 (3)	0.0347 (7)
C4	0.2409 (4)	0.5162 (4)	0.6472 (3)	0.0444 (8)
H4	0.203962	0.450956	0.622463	0.053*
C5	0.2608 (5)	0.4893 (4)	0.7747 (3)	0.0502 (9)
H5	0.235882	0.407553	0.834725	0.060*
C6	0.3174 (5)	0.5828 (4)	0.8139 (3)	0.0497 (9)
H6	0.329959	0.565499	0.900147	0.060*
C7	0.3547 (5)	0.7010 (4)	0.7240 (3)	0.0476 (8)
H7	0.394316	0.763611	0.749597	0.057*
C8	0.3348 (4)	0.7302 (4)	0.5952 (3)	0.0395 (7)
H8	0.361727	0.811312	0.535910	0.047*
C9	0.1602 (4)	0.7837 (3)	0.2024 (3)	0.0347 (7)
C10	0.1624 (5)	0.6221 (4)	0.1988 (3)	0.0495 (9)
H10A	0.081193	0.596215	0.271236	0.074*
H10B	0.274186	0.542724	0.204634	0.074*
H10C	0.133282	0.626000	0.118211	0.074*
C11	−0.0166 (4)	0.9079 (4)	0.1859 (3)	0.0511 (9)
H11A	−0.041458	0.904804	0.105717	0.077*
H11B	−0.019318	1.011123	0.183458	0.077*
H11C	−0.100091	0.885702	0.258270	0.077*
C12	0.2941 (4)	0.8167 (4)	0.0858 (3)	0.0419 (8)
H12A	0.265705	0.817405	0.005856	0.063*
H12B	0.404214	0.735475	0.094402	0.063*
H12C	0.296201	0.917840	0.084185	0.063*
C13	0.2354 (5)	1.1830 (4)	0.4164 (3)	0.0457 (8)
H13A	0.115473	1.243516	0.437481	0.069*
H13B	0.295589	1.253399	0.384511	0.069*
H13C	0.273949	1.112222	0.493349	0.069*
C14	0.2062 (5)	1.2154 (4)	0.1408 (3)	0.0528 (9)
H14A	0.235205	1.162900	0.067720	0.079*
H14B	0.262029	1.288802	0.119801	0.079*
H14C	0.085110	1.271523	0.159965	0.079*
C15	0.5104 (4)	0.9464 (4)	0.2456 (4)	0.0494 (9)
H15A	0.551479	0.884554	0.324307	0.074*
H15B	0.569795	1.016588	0.204339	0.074*
H15C	0.529884	0.877254	0.186961	0.074*

Source of material

All manipulations were carried out under argon using standard Schlenk techniques. The title complex was synthesized according to literature methods [6], [8], [9]. To a solution of trimethylsilylmethyltolulithium ((Me₃Si)PhCH₂Li) (6 mmol) in diethyl ether (20 ml), tert-butyl nitrile (6 mmol) was added at ca. 273 K and the solution was stirred for 15 min and then kept stirring for 5 h at room temperature. To this solution, ZnCl₂ (3 mmol) was added at ca. 200 K and the suspension was stirred for 15 min and then for 5 h at room temperature. The sovlent was removed under reduced pressure and then we used CH₂Cl₂ to extract the solid. The filtrate was concentrated under vacuum until colorless crystals of the title compound appeared.

Experimental details

All hydrogen atomes were added, using the standard procedures for riding atoms in the SHELX system.

Comment

Metal-η³-allyl complexes are well known and play an important role in many metal-mediated reactions [5]. Lappert and co-workers prepared various 1-azaallyl complexes including some main group element and transition metal [6], [7], [8], [9]. Many years ago we have got a example of η³-azaallyl cobalt complex [10]. As part of a subsequent investigation, we have prepared the title complex, and present its structure here (the Figure). The title compond shows not enlarged η³-coordination mode but a coordination of the N atoms to Zn. Thus it is a comparing object to study the tranformation between η³-carbon coordination to a coordination of the amido nitrogen. The centrosymmetric title complex contains two amido ligands bound to the Zn, with Zn···N bond length of 1.842(2)Å. The two ligands form a perfect straight line (N/Zn/N′) due to symmetry (the Figure).

Corresponding author: Hong-Bo Tong, Institute of Applied Chemistry, Shanxi University, Wucheng Rd. 92#, Taiyuan, Shanxi Province, P. R. China, E-mail: tong@sxu.edu.cn

Funding source: Key Research and Development Projects in Shanxi Province

Award Identifier / Grant number: 201803D121040

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: Key Research and Development Projects in Shanxi Province No. 201803D121040.
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2021-02-07

Accepted: 2021-02-26

Published Online: 2021-03-15

Published in Print: 2021-07-27

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