Crystal structure of 1,1′-(1,4-phenylenebis(methylene))bis(pyridin-1-ium) bis(1,2-dicyanoethene-1,2-dithiolato-k2S:S)zinc(II), C26H18N6ZnS4

Wei-Hong Yan; Xue-Guo Liu; Ming-Le Shen; Hui-Yan Pan

doi:10.1515/ncrs-2020-0624

Open Access Published by De Gruyter (O) January 20, 2021

Crystal structure of 1,1′-(1,4-phenylenebis(methylene))bis(pyridin-1-ium) bis(1,2-dicyanoethene-1,2-dithiolato-k²S:S)zinc(II), C₂₆H₁₈N₆ZnS₄

Wei-Hong Yan , Xue-Guo Liu , Ming-Le Shen and Hui-Yan Pan

From the journal Zeitschrift für Kristallographie - New Crystal Structures

https://doi.org/10.1515/ncrs-2020-0624

Abstract

C₂₆H₁₈N₆ZnS₄, triclinic, P1‾ (no. 2), a = 9.4677(13) Å, b = 12.0147(17) Å, c = 13.571(3) Å, α = 102.907(3)°, β = 102.302(3)°, γ = 110.419(2)°, V = 1336.7(4) Å³, Z = 2, R_gt(F) = 0.0441, wR_ref(F²) = 0.1202, T = 296(2) K.

CCDC no.: 2048820

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:	Yellow block
Size:	0.22 × 0.21 × 0.18 mm
Wavelength:	Mo Kα radiation (0.71073 Å)
μ:	1.26 mm⁻¹
Diffractometer, scan mode:	φ and ω
θ_max, completeness:	28.3°, >99%
N(hkl)_measured, N(hkl)_unique, R_int:	9681, 6567, 0.093
Criterion for I_obs, N(hkl)_gt:	I_obs > 2 σ(I_obs), 5260
N(param)_refined:	334
Programs:	SHELX [1], Bruker [2]

Table 2:

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

Atom	x	y	z	U_iso*/U_eq
C1	0.9451 (3)	0.2105 (2)	0.05814 (18)	0.0456 (5)
C2	0.9456 (2)	0.2330 (2)	0.16656 (17)	0.0416 (4)
C3	0.8896 (3)	0.3176 (2)	0.20736 (18)	0.0427 (5)
C4	0.8312 (3)	0.3768 (2)	0.13851 (19)	0.0517 (6)
C5	1.1081 (3)	0.1708 (2)	0.70883 (18)	0.0462 (5)
C6	1.0242 (3)	0.1611 (2)	0.60428 (16)	0.0398 (4)
C7	0.8665 (3)	0.08420 (19)	0.55806 (17)	0.0402 (4)
C8	0.7812 (3)	0.0135 (2)	0.61560 (19)	0.0456 (5)
C9	0.8185 (3)	0.3409 (3)	0.6839 (3)	0.0652 (7)
H9	0.9070	0.3806	0.6648	0.078*
C10	0.8384 (4)	0.3195 (3)	0.7798 (3)	0.0754 (9)
H10	0.9401	0.3441	0.8256	0.090*
C11	0.7076 (4)	0.2615 (3)	0.8076 (2)	0.0656 (7)
H11	0.7197	0.2483	0.8733	0.079*
C12	0.5599 (3)	0.2233 (3)	0.7382 (2)	0.0581 (6)
H12	0.4700	0.1823	0.7553	0.070*
C13	0.5450 (3)	0.2456 (2)	0.6431 (2)	0.0508 (5)
H13	0.4442	0.2188	0.5952	0.061*
C14	0.6497 (4)	0.3285 (3)	0.5137 (2)	0.0600 (7)
H14A	0.5848	0.2492	0.4569	0.072*
H14B	0.7521	0.3634	0.5030	0.072*
C15	0.5708 (3)	0.4173 (2)	0.50768 (19)	0.0458 (5)
C16	0.6505 (3)	0.5423 (2)	0.5690 (2)	0.0504 (5)
H16	0.7525	0.5712	0.6161	0.060*
C17	0.4190 (3)	0.3753 (2)	0.4385 (2)	0.0494 (5)
H17	0.3636	0.2911	0.3969	0.059*
C18	0.3202 (3)	0.3055 (3)	0.0460 (2)	0.0557 (6)
H18	0.2415	0.2608	−0.0198	0.067*
C19	0.3896 (4)	0.4352 (3)	0.0796 (3)	0.0688 (8)
H19	0.3565	0.4782	0.0372	0.083*
C20	0.5072 (3)	0.4997 (3)	0.1754 (3)	0.0641 (7)
H20	0.5559	0.5869	0.1986	0.077*
C21	0.5525 (3)	0.4348 (3)	0.2370 (2)	0.0611 (6)
H21	0.6326	0.4774	0.3025	0.073*
C22	0.4805 (3)	0.3087 (2)	0.20223 (18)	0.0516 (5)
H22	0.5109	0.2649	0.2448	0.062*
C23	0.2920 (3)	0.1048 (2)	0.0721 (2)	0.0613 (7)
H23A	0.1937	0.0736	0.0139	0.074*
H23B	0.2664	0.0767	0.1303	0.074*
C24	0.4017 (3)	0.0515 (2)	0.0355 (2)	0.0462 (5)
C25	0.4100 (3)	0.0389 (2)	−0.0667 (2)	0.0539 (6)
H25	0.3491	0.0643	−0.1124	0.065*
C26	0.4905 (3)	0.0118 (2)	0.1012 (2)	0.0540 (6)
H26	0.4841	0.0188	0.1696	0.065*
N1	0.6731 (2)	0.30538 (17)	0.61782 (15)	0.0449 (4)
N2	0.3663 (2)	0.24471 (17)	0.10803 (14)	0.0407 (4)
N3	0.7826 (3)	0.4239 (3)	0.0834 (2)	0.0769 (8)
N4	0.9460 (3)	0.1911 (3)	−0.02791 (18)	0.0636 (6)
N5	0.7066 (3)	−0.0423 (2)	0.6590 (2)	0.0623 (6)
N6	1.1847 (3)	0.1848 (2)	0.79231 (17)	0.0673 (6)
S1	1.01499 (8)	0.14502 (6)	0.23146 (5)	0.04983 (15)
S2	0.88203 (8)	0.35786 (6)	0.33647 (5)	0.05154 (16)
S3	1.14199 (6)	0.25819 (6)	0.54831 (5)	0.04838 (15)
S4	0.75176 (7)	0.06525 (6)	0.43227 (5)	0.04942 (15)
Zn1	0.95002 (3)	0.20276 (2)	0.38601 (2)	0.04353 (10)

Source of material

All reagents and chemicals were purchased from commercial sources and used without further purification. The starting materials disodium maleonitriledithiolate and 1,4-bis(methylpyridinium benzene bromide were synthesized following the literature procedures [3], [, 4]. An aqueous solution (10 mL) of 1,1′-(1,4-phenylenebis(methylene))bis(pyridin-1-ium) dibromide (BisPyBr₂) (0.0842 g, 0.2 mmol) was added slowly to an aqueous solution (15 mL) of disodium maleonitriledithiolate (0.0741 g, 0.4 mmol) and ZnCl₂ (0.0277 g, 0.2 mmol). The mixture was stirred at room temperature for several minutes. A yellow precipitate was filtered off, washed by water and dried under vacuum. The precipitate was solved in DMF with ether diffusion yielding yellow crystals after two weeks.

Experimental details

Absorption corrections were applied by using the multi-scan method. Hydrogen atoms were located in difference electron density maps, and treated as riding atoms. The U_iso values of the hydrogen atoms were set to 1.2U_eq(C).

Comment

The maleonitriledithiolate (mnt) ligand is most often used for special structures and has great potential in diversified applications, such as conducting, magnetic materials, dyes and non-linear optics [5], [6], [7], [8], and so on. Compared with the [Ni(mnt)₂]ⁿ⁻ complexes [9], [10], [11], the [Zn(mnt)₂]²⁻ complexes are less studied.

The title complex crystallizes in triclinic P1‾ space group. The asymmetric unit of complex consists of one [Zn(mnt)₂]²⁻ and two halves of the BisPy dication. The Zn²⁺ ion is surrounded by four sulfur atoms from two mnt²⁻ ligands, and its coordination geometry is a slightly distorted tetrahedron. The Zn–S bond lengths range from 2.3222 (7) to 2.3561 (6) Å, and the S–Zn–S bond angles are in the range of 92.76 (2)–123.67 (3). All of these geometric parameters are comparable to that in the reported [Zn(mnt)₂]²⁻ complex [12]. The anions and cations form segregated columns. Weak C–H⃛N interactions are observed in the title structure [13]. A supramolecular network structure is thus constructed through weak intermolecular interactions.

Corresponding author: Wei-Hong Yan, School of Biology and Chemical Engineering, Nanyang Institute of Technology, Nanyang473004, China, E-mail: yyu_yu@163.com

Funding source: Scientific and Technological Research Projects of Henan Province

Award Identifier / Grant number: 182102311077

Funding source: National Natural Science Foundation of China

Award Identifier / Grant number: 21776063, U1704127

Author contribution: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: The Scientific and Technological Research Projects of Henan Province (182102311077), the National Natural Science Foundation of China (21776063, U1704127).
Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2020-12-07

Accepted: 2020-12-23

Published Online: 2021-01-20

Published in Print: 2021-05-26

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