Startseite Crystal structure of poly[μ3-diiodido-[μ2-di(1H-pyrazol-1-yl)methane-κ2N,N′)]dicopper(I)], C7H8Cu2I2N4
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Crystal structure of poly[μ3-diiodido-[μ2-di(1H-pyrazol-1-yl)methane-κ2N,N′)]dicopper(I)], C7H8Cu2I2N4

  • Yidong Zhang und Chao Feng ORCID logo EMAIL logo
Veröffentlicht/Copyright: 5. Februar 2024

Abstract

C7H8Cu2I2N4, monoclinic, I2 (no. 5), a = 9.3131(14) Å, b = 4.2354(6) Å, c = 14.959(2) Å, β = 92.583(13)°, V = 2143.4(2) Å3, Z = 2, Rgt(F) = 0.0277, wRref(F 2 ) = 0.0672, T = 293 K.

CCDC no.: 2326067

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: Colorless needle
Size: 0.26 × 0.23 × 0.18 mm
Wavelength: MoKα radiation (0.71073 Å)
μ: 8.82 mm−1
Diffractometer, scan mode: Xcalibur, ω
θmax, completeness: 29.5°, >99 %
N(hkl)measured, N(hkl)unique, Rint: 1497, 1056, 0.021
Criterion for Iobs, N(hkl)gt: Iobs > 2 σ(Iobs), 970
N(param)refined: 70
Programs: SHELX [1], [2]
Table 2:

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

Atom x y z Uiso*/Ueq
I1 0.85196 (4) 0.53854 (2) 0.86468 (3) 0.02960 (16)
Cu1 0.80513 (10) 0.5194 (7) 0.68420 (7) 0.0431 (3)
N1 1.0046 (7) 0.6010 (19) 0.6376 (4) 0.029 (2)
N2 1.0739 (6) 0.4762 (18) 0.5677 (4) 0.026 (2)
C1 1.2128 (7) 0.565 (5) 0.5684 (6) 0.038 (2)
H1 1.2811 0.5036 0.5284 0.046*
C2 1.2330 (10) 0.765 (2) 0.6402 (6) 0.037(2)
H2 1.3173 0.8703 0.6576 0.044*
C3 1.1010 (10) 0.779 (2) 0.6820 (6) 0.034 (2)
H3 1.0839 0.8951 0.7332 0.041*
C4 1.0000 0.287(3) 0.5000 0.027(3)
H4Aa 0.9310 0.1519 0.5282 0.033*
H4Ba 1.0690 0.1519 0.4718 0.033*
  1. a

    Occupancy: 0.5.

1 Source of material

All chemical reagents were purchased from commercial sources and used without further purification. A mixture of CuI (0.0381 g, 0.2 mmol) and di(1H-pyrazol-1-yl)methane (0.296 g, 0.2 mmol) were dissolved in 15 mL MeCN, and the mixture was stirred at room temperature for 5 min. Subsequently, the resulting solution was transferred to a Teflon-lined autoclave (20 mL) and heated at 140 °C for 5 days. Afterward, the mixture was allowed to cool down naturally. Finally, colorless needle crystals were obtained by filtration.

2 Experimental details

The crystal structure was solved using the Shelxt [1] program and refined with Shelxl2014/7 [2]. Anisotropic thermal parameters were applied to refine all non-hydrogen atoms. All H atoms were included in calculated positions and refined as riding atoms, with C–H = 0.90–0.97 Å with 1.2 Ueq(C) for all H atoms. As a half of reciprocal space diffraction data were collected only using a four-circle diffractometer, Friedel pair coverage is low in this determination [3], [4].

3 Comment

In recent decades, luminescent metal complexes have been widely studied due to their potential applications in OLED and other fields, such as complexes of precious metals Ir(III), Pt(II), Os(II) [5]. However, their high cost, toxicity, and environmental pollution have led to widespread attention to complexes which are low cost, low environmental pollution, and tunable luminescence.

Cu(I) complexes are a type of metal organic functional materials formed by coordination bonds between inorganic or organic ligands and copper atoms. Due to its rich coordination modes, Cu(I) complexes have been attached more and more attentions [6]. In order to reduce the steric hindrance between ligands, Cu(I) complexes mostly exist in a four coordinated mode. Different coordination hindrance results in different degrees of distortion of the central structure of the formed complexes. Generally, the larger the steric hindrance, the more twisted the structure is. When the steric hindrance of the ligand is large, it is difficult to form a tetrahedral configuration, and a quasi planar configuration is usually formed in a three coordinated mode. In addition, with the in-depth study of cuprous halide complexes, it has been found that halogen atoms can form cuprous halide cluster centers by connecting with two or more copper atoms, and then combine with different organic ligands to form zero dimensional, one-dimensional, two-dimensional, or three-dimensional cluster structures [7]. After decades of exploration, researchers have gained a deeper understanding of cuprous halide complexes, no longer just focusing on the preparation of new complexes, but also on the study of their structure-activity relationships. They are gradually being applied in fields such as organic EL devices, optical sensors, and electrochemical batteries due to their rich structure, electronic transition types, and multi-color luminescence [8], [9].

Based on the above discussion, we have selected the di(1H-pyrazol-1-yl)methane ligand and cuprous iodide to prepare a novel polymer with sql topological structure by solvothermal method. X-ray single crystal diffraction reveals that the asymmetric unit consists of one Cu(I) ion, half a ligand molecule and one iodine ion. The complex is bridged by iodine ions and di(1H-pyrazol-1-yl)methane ligands to form a two-dimensional structure with a sql topological configuration. The central Cu(I) ion gives a distorted tetrahedron coordination configuration [CuI3N], the Cu(I) ion is coordinated to one N atom from the di(1H-pyrazol-1-yl)methane ligand and three μ3-iodine atoms. In the tetrahedron, the bond length of Cu–N is 2.042(6) Å, and Cu–I is 2.594(2)–2.723(3) Å, respectively. Meanwhile, the bond angles of I–Cu–N and I–Cu–I are all fallen within the normal range. In the crystal structure, there exists an unconventional hydrogen bond C–H⋯I linking the title complex into a three-dimensional structure.


Corresponding author: Chao Feng, School of Materials and Chemical Engineering, Bengbu University, Bengbu 233030, P.R. China, E-mail:

Funding source: Special Fund for Science and Technology Program of Yancheng

Award Identifier / Grant number: (YCBK2023007)

Funding source: Industry–University–Research Collaboration of Bengbu University

Award Identifier / Grant number: (00013322)

  1. Author contributions: The author has accepted responsibility for the entire content of this submitted manuscript and approved submission.

  2. Research funding: This work was supported by Special Fund for Science and Technology Program of Yancheng (YCBK2023007) and Industry–University–Research Collaboration of Bengbu University (00013322).

  3. Conflict of interest statement: The author declares no conflicts of interest regarding this article.

References

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Received: 2023-12-18
Accepted: 2024-01-17
Published Online: 2024-02-05
Published in Print: 2024-04-25

© 2024 the author(s), published by De Gruyter, Berlin/Boston

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

Artikel in diesem Heft

  1. Frontmatter
  2. New Crystal Structures
  3. Solvothermal synthesis and crystal structure of aqua-tris(p-acetamidobenzoate-κ2O,O′)-(2,2′-bipyridine-κ2N,N′)terbium(III) - water - methanol (1/1/1)
  4. Crystal structure of hexaaquazinc(II) catena-poly[bis(1-(3-carboxyphenyl)-5-methyl-4-oxo-1,4-dihydropyridazine-3-carboxylato-κ2O,O′)-bis(μ2-1-(3-carboxyphenyl)-5-methyl-4-oxo-1,4-dihydropyridazine-3-carboxylato-κ2O:O′)trizinc(II)] hexahydrate C26H36N4O20Zn2
  5. The crystal structure of valinyl-N-ium-4-(5-(thiophen-2-yl)isoxazol-3-yl)phenyl trifluoroacetate
  6. Crystal structure of bis(3,5-diisopropyl-1H-pyrazol-4-ammonium) tetrafluoroterephthalate, 2[C9H18N3][C8F4O4]
  7. Crystal structure of aqua-octakis(μ3-salicylato)-(1,10-phenanthroline)-(acetonitrile)-dicobalt(II)-trititanium(IV), C70H45N3O25Co2Ti3
  8. Crystal structure of catena-poly[aqua-(μ2-4,4′-diimidazole diphenyl ether-κ2N:N′)-(sulfato-κ1O)-cobalt(II)] – dimethylformamide (2/1), C39H37CoN9O8S
  9. Crystal structure of (5R,8R,9R,10R,12R, 13R,14R,17S)-2-(E-3-fluorobenzylidene)-12-hydroxy-4,4,8,10,14-pentamethyl-17-((R)-2,6,6-trimethyltetrahydro-2H-pyran-2-yl) hexadecahydro-3H-cyclopenta[a]phenanthren-3-one, C37H53FO3
  10. Crystal structure of (Z)-4-((4,5,6-trimethoxy-3-oxobenzofuran-2(3H)-ylidene)methyl)phenyl diphenylphosphinate, C30H25O7P
  11. Crystal structure of 3-((5-methylpyridin-2-yl)amino)-1-phenylpropan-1-one, C15H16N2O
  12. The crystal structure of (R)-9-(5-methoxy-2-methyl-2,3-dihydro-1H-cyclopenta[a]naphthalen-1-ylidene)-9H-thioxanthene, C28H22OS
  13. Crystal structure of diaqua-bis[1-(1-(hydroxymethyl)-1H-pyrazol-3-yl)-5-methyl-1H-1,2,3-triazole-4-carboxylato-κ2N,O)] manganese(II), C16H20MnN10O8
  14. The crystal structure of t-butyl 7-[4-(4-fluorophenyl)-2-[(methanesulfonyl)(methyl)amino]-6-(propan-2-yl)pyrimidin-5-yl]-3,5-dihydroxyhept-6-enoate, C26H36FN3O6S
  15. The crystal structure of samarium sulfate pentahydrate, Sm2(SO4)3(H2O)5
  16. The crystal structure of [triaqua-(8-carboxymethoxy-quinoline-2-carboxylate-κ 4 N,O,O,O)-zinc(II)] monohydrate, C12H15NO9Zn
  17. The crystal structure of 2,3-difluoro-11H-benzo-[4,5]imidazo[2,1-a]isoindol-11-one, C14H6F2N2O
  18. The crystal structure of 2,3-di(9H-carbazol-9-yl)-9H-fluoren-9-one, C37H22N2O
  19. The crystal structure of 5-(2-chloro-3-(3,6-di-tert-butyl-9H-carbazol-9-yl)phenyl)-10,11-dihydro-5H-dibenzo[b,f]azepine, C40H39ClN2
  20. Crystal structure of 2-bromo-1-hydroxy-3-(3-methylbut-2-enyloxy)-9H-xanthen-9-one, C18H15BrO4
  21. Crystal structure of bis(μ2-benzenesulfonato-κ2O:O′)-bis(μ2-6,6′-((ethane-1,2-diylbis(azaneylylidene))bis(methaneylylidene))-bis(2-methoxyphenolato-κ6O,O′:O′,N,N′,O′′:O′′,O′′′))disodium(I)dicopper(II)
  22. The crystal structure of (E)-1,2-bis(benzo[e][1,2]azaborinin-2(1H)-yl)ethene, C18H16B2N2
  23. Crystal structure of 3-oxo-urs-12-en-28-benzyl ester, C37H52O3
  24. The crystal structure of ethyl (E)-1-chloro-3-(4-chloro-1-methyl-1H-indole-2-carbonyl)-4-oxo-2-phenylcyclooct-2-ene-1-carboxylate, C27H25Cl2NO4
  25. The crystal structure of 4,4′-((5-bromo-2-iodo-1,3-phenylene)bis(oxy))bis(tert-butylbenzene) ─ ethanol (2/1), C26H28BrIO2
  26. Crystal structure of (E)-1-(4-(benzyloxy)-2-hydroxyphenyl)-3-(dimethylamino)prop-2-en-1-one, C18H19NO3
  27. The crystal structure of N1,N3-bis(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)\ propanediamide hydrate, C25H26N6O4, 2(H2O)
  28. The crystal structure of 2,5-bis[(1,5-dimethyl-3-oxo-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)amino]cyclohexa-2,5-diene-1,4-dione, C28H26N6O4
  29. Crystal structure of 3,4-bis[2-(hydroxymethyl)-pyrrolidin-1-yl] cyclobut-3-ene-1,2-dione hydrate, C14H22N2O5
  30. The crystal structure of 2-(3,4–dichlorobenzyl)-1H-benzimidazole, C14H10Cl2N2
  31. The crystal structure of 2-(2-((4,6-dimethoxypyrimidin-2-yl)oxy)phenyl)-4-(piperidin-1-yl)-5H-chromeno[2,3-d]pyrimidine, C28H27N5O4
  32. The crystal structure of 6-(benzofuran-2-yl)-2-oxo-4,5-diphenyl-3,4-dihydro-2H-pyran-3-carbonitrile, C26H17NO3
  33. Crystal structure of N-(4-bromobenzyl)-3-(difluoromethyl)-1-methyl-N-(pyridin-2-yl)-1H-pyrazole-4-carboxamide, C18H15BrF2N4O
  34. The crystal structure of the host-guest complex: N-{5-[2-(2,6-dimethylphenoxy)acetamido]-4-hydroxy-1,6-diphenylhexan-2-yl}-3-methyl-2-(2-oxo-1,3-diazinan-1-yl)butanamide-diethyl ether (2/1)
  35. The crystal structure of (Z)-4-amino-N-(1-(4-hydroxyphenyl)propylidene)benzohydrazide, C16H17N3O2
  36. The crystal structure of diethyl 1,4-dihydro-2,6-dimethyl-4-(3-cyanophenyl)-3,5-pyridinedicarboxylate, C20H22N2O4
  37. Crystal structure of 3-(5-((4-(difluoromethoxy)phenyl) sulfonyl)-3,4,5,6-tetrahydropyrrolo[3,4-c]pyrrol-2(1H)-yl) oxetane-3-carboxamide, C17H19F2N3O5S
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  48. Crystal structure of 3-amino-N′-hydroxy-1H-pyrazole-4-carboximidamide, C4H7N5O
  49. The crystal structure of 1,3-diacetyltetrahydroimidazo[4,5-d]imidazole-2,5(1H,3H)-dione, C8H10O4N4
  50. Crystal structure of catena-poly[aqua-(μ2-1,4-diazabicyclo[2.2.2]octane-k2N: N′)-bis(sorbato-κ1O)-copper(II), C18H28CuN2O5
  51. Crystal structure of catena-poly[triaqua-(μ2 -1-(4-carboxylatophenyl)-4-oxo-1,4-dihydropyridazine-3-carboxylato-κ3O,O′:O′′)manganese(II)], C12H12N2O8Mn
  52. The crystal structure of [hexaaquamagnesium(II)] 4-[(pyridine-4-carbonyl)-amino]-phthalate trihydrate, C14H26N2O14Mg
  53. Crystal structure of 1-(p-tolylphenyl)-4-(2-furoyl)-3-methyl-1H-pyrazol-5-ol, C16H14N2O3
  54. The crystal structure of bis(1,4,7,10,13-pentaoxacyclopentadecane)-potassium(I) dichloridocopper(I), C20H40Cl2CuKO10
  55. The crystal structure of tris(tetra-n-butylammonium) hexanitrato-κ2O,O′-lanthanium(III) C48H108N9O18La
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