Home Crystal structure of dimethylammonium poly[μ4-1,1′-(1,4- phenylenebis(methylene))bis(1H-pyrazole-3,5-dicarboxylato-κ6 N,O:O′:N′,O″:O‴) manganese(II)], C22H26MnN6O8
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Crystal structure of dimethylammonium poly[μ4-1,1′-(1,4- phenylenebis(methylene))bis(1H-pyrazole-3,5-dicarboxylato-κ6 N,O:O′:N′,O″:O‴) manganese(II)], C22H26MnN6O8

  • Yu-Pei Xia ORCID logo EMAIL logo and Lu-Lu Han
Published/Copyright: August 12, 2022

Abstract

C22H26MnN6O8, monoclinic, P21/n (no. 14), a = 11.1483(9) Å, b = 10.5789(8) Å, c = 11.8538(10) Å, β = 115.883(2)°, V = 1257.76(18) Å3, Z = 2, R gt(F) = 0.0585, wR ref(F 2) = 0.1614, T = 298 K.

CCDC no.: 2169192

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: Pink block
Size: 0.40 × 0.34 × 0.13 mm
Wavelength: Mo Kα radiation (0.71073 Å)
μ: 0.58 mm−1
Diffractometer, scan mode: Bruker D8 Advance, φ and ω
θ max, completeness: 28.3°, >99%
N(hkl)measured, N(hkl)unique, R int: 7928, 3102, 0.093
Criterion for I obs, N(hkl)gt: I obs > 2 σ(I obs), 1997
N(param)refined: 171
Programs: Bruker [1], Olex2 [2], SHELX [3, 4]
Table 2:

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

Atom x y z U iso*/U eq
Mn1 0.500000 0.000000 0.000000 0.0276 (2)
O1 0.5874 (2) 0.0943 (2) 0.1794 (2) 0.0411 (5)
O2 0.4356 (2) 0.1442 (3) 0.2452 (3) 0.0709 (9)
O3 0.6645 (2) 0.5762 (2) 0.5616 (3) 0.0556 (7)
O4 0.85889 (18) 0.59569 (17) 0.55235 (19) 0.0333 (5)
N1 0.7660 (2) 0.2728 (2) 0.3522 (2) 0.0269 (5)
N2 0.8190 (2) 0.3745 (2) 0.4260 (2) 0.0274 (5)
C1 0.5453 (3) 0.1561 (3) 0.2437 (3) 0.0387 (7)
C2 0.6355 (3) 0.2566 (3) 0.3279 (3) 0.0301 (6)
C3 0.6043 (3) 0.3534 (3) 0.3890 (3) 0.0338 (7)
H3 0.522806 0.367925 0.390611 0.041*
C4 0.7203 (3) 0.4247 (2) 0.4476 (3) 0.0282 (6)
C5 0.7496 (3) 0.5418 (3) 0.5266 (3) 0.0325 (6)
C6 0.8573 (3) 0.1975 (3) 0.3186 (3) 0.0312 (6)
H6A 0.922395 0.253603 0.311274 0.037*
H6B 0.806567 0.158775 0.237234 0.037*
C7 0.9303 (3) 0.0947 (3) 0.4130 (3) 0.0304 (6)
C8 0.8738 (3) −0.0227 (3) 0.4079 (3) 0.0388 (7)
H8 0.788632 −0.039207 0.345667 0.047*
C9 1.0579 (3) 0.1164 (3) 0.5058 (3) 0.0409 (8)
H9 1.098132 0.194462 0.510399 0.049*
N3 0.7753 (4) 0.6969 (4) 0.7848 (4) 0.0873 (13)
H3A 0.744893 0.664582 0.707957 0.105*
H3B 0.715677 0.753327 0.783941 0.105*
C10 0.7813 (9) 0.5947 (7) 0.8708 (6) 0.146 (3)
H10A 0.694754 0.556848 0.842913 0.220*
H10B 0.808951 0.628414 0.953628 0.220*
H10C 0.844104 0.531905 0.872210 0.220*
C11 0.9000 (5) 0.7638 (8) 0.8119 (6) 0.151 (3)
H11A 0.889625 0.813400 0.740415 0.226*
H11B 0.970467 0.703550 0.830176 0.226*
H11C 0.921644 0.818278 0.882933 0.226*

Source of material

All materials were commercially purchased and used as received. MnCl2·4H2O (0.0198 g, 0.1 mmol), 1,1′-(1,4-phenylenebis(methylene))bis(1H-pyrazole-3,5-dicarboxylic acid) (H4L, 0.0207 g, 0.05 mmol), DMF/H2O (8 mL, 4:4, v/v) and two drops of HCl were mixed in a 20 mL capped vial. The vial was transferred to a 100 °C oven for three days and cooled to room temperature at a rate of 10 °C/h. Pink needle crystals of the title complex were obtained, yielding 47% (based on the ligand).

Experimental details

The following operations were executed throughout the OLEX2 software. The initial structure of the complex was solved by intrinsic phasing with the SHELXT program. The SHELXL program with was applied to refine the structure. The hydrogen atoms were placed in their idealized positions with isotropic thermal parameters.

Comment

As a multidentate ligand, 1,1′-1,4-(phenylenebis(methylene))- bis(1H-pyrazole-3,5-dicarboxylic acid) (H4L), bearing two kinds of potential coordinated sites (O and N), has been exploited to build metal complexes [5], [6], [7]. Obviously, apart from the multidentate property, the outstanding flexibility nature of H4L can extend the family of the H4L-based metal complexes. With this in mind, the title Mn(II)-complex was synthesized via one-pot synthesis. The complex crystallizes in the monoclinic system in the space group P21/n.

The asymmetric unit consists of one half of deprotonated L4- ligand (around an inversion center), one half of Mn(II) ion (on an inversion center) and one dimethylammonium cation. The Mn(II) ion is six-coordinated with four carboxylic oxygen (O1, O11 − x, −y, −z , O41.5 − x, −0.5 + y, 0.5 − z, O4−0.5 + x, 0.5 − y, −0.5 + z ) derived from four L4- ligands and two nitrogen atoms (N21.5 − x, −0.5 + y, 0.5 − z , N2−0.5 + x, 0.5 − y, −0.5 + z ) derived from two pyrazole rings. The Mn–O and Mn–N bonds are within 2.158(2)–2.249(2) Å, which are parallel to the other reported Mn(II)-complexes with similar coordination environments [8, 9]. Each L4- ligand is connected with four Mn(II) ions to form two-dimensional layers (see the figure). The isolated dimethylammonium cations not only balanced the charge of the complex, but also play important roles in forming the three-dimensional network, as the 2D layers are further connected by the cations via N—H···O hydrogen bonding interactions (N3—H3A···O3, N3—H3B···O21 − x, 1 − y, 1 − z ).


Corresponding author: Yu-Pei Xia, College of Chemistry and Chemical Engineering, Weifang University, Weifang, Shandong 261061, P. R. China, E-mail:

Funding source: Doctoral Program of Weifang University

Award Identifier / Grant number: 2021BS09

Funding source: The Research Fund for the Doctoral Program of Weifang University

Award Identifier / Grant number: 2021BS09

Acknowledgments

Special thanks are given to Lu-Lu Han for her kind assistance with the structure discussion of the complex.

  1. Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: This work was supported by the Research Fund for the Doctoral Program of Weifang University (NO. 2021BS09).

  3. Conflict of interest statement: The authors declare no conflicts of interest regarding this article.

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Received: 2022-06-30
Accepted: 2022-07-22
Published Online: 2022-08-12
Published in Print: 2022-10-26

© 2022 the author(s), published by De Gruyter, Berlin/Boston

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

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