Home Crystal structure of polybis(μ 4-3,5-dicarboxylatopyrazol-1-yl)-bis(N,N-dimethylformamide)tri-copper(II)–acetonitrile (1/2), C20H22Cu3N8O10
Article Open Access

Crystal structure of polybis(μ 4-3,5-dicarboxylatopyrazol-1-yl)-bis(N,N-dimethylformamide)tri-copper(II)–acetonitrile (1/2), C20H22Cu3N8O10

  • Yan-Qing Wang ORCID logo EMAIL logo , Wen-Qing Yan , Li-Xue Nie , Ping-Ping Luan and Chao-Qun Li
Published/Copyright: September 5, 2023

Abstract

C20H22Cu3N8O10, monoclinic, C2/c (no. 15), a = 12.0766(11) Å, b = 16.2778(14) Å, c = 14.7605(13) Å, β = 97.8580(10), V = 2874.4(4) Å3, Z = 4, R gt(F) = 0.0420, wR ref (F 2) = 0.0988, T = 298.15 K.

CCDC no.: 2267389

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: Blue block
Size: 0.18 × 0.17 × 0.12 mm
Wavelength: Mo Kα radiation (0.71073 Å)
μ: 2.26 mm−1
Diffractometer, scan mode: Bruker SMART CCD 6000, φ and ω
θ max, completeness: 25.3°, >99 %
N(hkl)measured , N(hkl)unique, R int: 7417, 2630, 0.053
Criterion for I obs, N(hkl) gt: I obs > 2 σ(I obs), 1939
N(param)refined: 189
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
C1 0.6408 (3) 0.9050 (2) 0.3210 (3) 0.0284 (9)
C2 0.7073 (4) 0.8279 (2) 0.3236 (3) 0.0318 (10)
C3 0.7532 (4) 0.7755 (2) 0.2635 (3) 0.0330 (10)
H3 0.752597 0.781782 0.200846 0.040*
C4 0.7994 (4) 0.7124 (2) 0.3185 (3) 0.0313 (10)
C5 0.8639 (4) 0.6356 (2) 0.3114 (3) 0.0301 (10)
C6 0.5815 (5) 0.5752 (4) 0.4138 (4) 0.0641 (15)
H6 0.565399 0.631057 0.411143 0.077*
C7 0.5206 (7) 0.4368 (4) 0.3809 (5) 0.097 (2)
H7A 0.549252 0.420900 0.325935 0.146*
H7B 0.451781 0.408298 0.384645 0.146*
H7C 0.573987 0.423167 0.432970 0.146*
C8 0.3870 (5) 0.5546 (5) 0.3430 (5) 0.105 (3)
H8A 0.333900 0.533051 0.379588 0.158*
H8B 0.368172 0.536208 0.280970 0.158*
H8C 0.385488 0.613522 0.344660 0.158*
C9 0.8544 (5) 0.3952 (3) 0.4851 (4) 0.0733 (18)
H9A 0.903427 0.433399 0.460993 0.110*
H9B 0.849428 0.408498 0.547746 0.110*
H9C 0.781487 0.398217 0.450039 0.110*
C10 0.8969 (6) 0.3150 (4) 0.4799 (5) 0.089 (2)
Cu1 0.82569 (5) 0.64141 (3) 0.49417 (3) 0.0404 (2)
Cu2 1.000000 0.52545 (4) 0.250000 0.02145 (18)
N1 0.7266 (3) 0.7964 (2) 0.4080 (2) 0.0425 (10)
N2 0.7827 (3) 0.7264 (2) 0.4055 (2) 0.0403 (10)
N3 0.5003 (4) 0.5253 (3) 0.3794 (3) 0.0711 (14)
N4 0.9345 (8) 0.2527 (5) 0.4762 (6) 0.173 (4)
O1 0.6150 (2) 0.92923 (16) 0.39738 (17) 0.0344 (7)
O2 0.6123 (2) 0.94018 (16) 0.24630 (17) 0.0314 (7)
O3 0.8874 (2) 0.61283 (15) 0.23483 (17) 0.0304 (7)
O4 0.8944 (2) 0.59660 (16) 0.38576 (17) 0.0343 (7)
O5 0.6750 (3) 0.5560 (2) 0.4487 (3) 0.0635 (10)

1 Source of materials

The 3,5-pyrazoledicarboxylic acid (H3PDC) was purchased from Anhui Zesheng Technology Co., Ltd. Other reagents were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. Copper(II) chloride dihydrate (CuCl2·2H2O, 0.0170 g, 0.1 mmol) and H3PDC (0.0174 g, 0.1 mmol) were dissolved in 8 mL N,N–dimethylformamide (DMF) and 4 mL acetonitrile (CH3CN). The mixture was then transfered to a 20 mL stainless steel vessel, heated to 120 °C for 3 days and cooled to room temperature at a rate of 15 °C/h. Clear light blue block crystals of the title complex were obtained, yielding 39 % (based on the ligand).

2 Experimental details

The initial structure of the title complex was solved by the Shelxt program. The refinement process was performed by the SHELXL program. The H-atoms were placed in their idealized positions with isotropic thermal parameters.

3 Comment

As a robust multidentate ligand containing both N- and O-coordination sites, 3,5-pyrazoledicarboxylic acid (H3PDC) has been applied to build metal complexes. However, the reported Cu(II)-complexes are either monometallic structures with low dimensionality or three-dimensional structures obtained by mixing metal ions or ligands [5], [6], [7], [8]. Hence, to extend the family of the monometallic Cu(II)–H3PDC-based structures with high-dimensional, the title 3D Cu(II)-complex was synthesized under hydrothermal condition.

The asymmetric unit contains one and a half copper(II) ions, one deprotonated H3PDC ligand, one coordinated DMF molecule and one free CH3CN molecule. The Cu1(II) and Cu2(II) display two different coordination modes. Cu1(II) is penta-coordinated, bonded with three O-atoms (O4, O5, O13/2−x,3/2−y,1−z ) and two N-atoms (N2, N13/2−x,3/2−y,1−z ). Unlike Cu1(II), Cu2(II) is tetra-coordinated, bonded with four O-atoms (O3, O23/2−x,−1/2+y,1/2−z , O21/2+x,−1/2+y,z , O32−x,y,1/2−z ). The distances of Cu–O and Cu–N are in the range of 1.946(3) – 2.315(4) Å and 1.926(3) – 1.938(3) Å, respectively. The bond lengths are comparable to the reported H3PDC-based crystal structures [9], [10], [11]. It is worth noting that the hydrogen atom belonging to the nitrogen atom (N1 or N2) of the ligand is also deprotonated. Two deprotonated H3PDC ligands, two Cu1 and two DMF molecules formed a [Cu2(H3PDC)2(DMF)2] unit. Those units are further linked by Cu2 and finally resulted in a 3D supermolecular network.


Corresponding author: Yan-Qing Wang, College of Chemistry and Chemical Engineering, Weifang University, Weifang, Shandong 261061, P.R. China, E-mail:

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

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

  3. Research funding: This work was supported by the Shandong Province Natural Science Foundation (No. ZR2021QB053), and research startup funds of Weifang University (No. 196100040020).

References

1. BRUKER. Saint and Sadabs; Bruker AXS Inc: Madison, Wisconsin, USA, 2000.Search in Google Scholar

2. Dolomanov, O. V., Bourhis, L. J., Gildea, R. J., Howard, J. A. K., Puschmann, H. OLEX2: a complete structure solution, refinement and analysis program. J. Appl. Crystallogr. 2009, 42, 339–341; https://doi.org/10.1107/s0021889808042726.Search in Google Scholar

3. Sheldrick, G. M. Crystal structure refinement with SHELXL. Acta Crystallogr. 2015, C71, 3–8; https://doi.org/10.1107/s2053229614024218.Search in Google Scholar

4. Sheldrick, G. M. SHELXTL – integrated space-group and crystal-structure determination. Acta Crystallogr. 2015, A71, 3–8; https://doi.org/10.1107/s2053273314026370.Search in Google Scholar PubMed PubMed Central

5. King, P., Clérac, R., Anson, C. E., Powell, A. K. The building block approach to extended solids: 3,5-pyrazoledicarboxylate coordination compounds of increasing dimensionality. Dalton Trans. 2004, 852–861; https://doi.org/10.1039/b315067d.Search in Google Scholar PubMed

6. Zhou, X.-H., Peng, Y.-H., Du, X.-D., Wang, C.-F., Zuo, J.-L., You, X.-Z. New 3d-4f heterometallic coordination polymers based on pyrazole-bridged CuIILnIII dinuclear units and sulfate anions: syntheses, structures, and magnetic properties. Cryst. Growth Des. 2008, 9, 1028–1035; https://doi.org/10.1021/cg800848n.Search in Google Scholar

7. Yang, T. H., Silva, A. R., Shi, F. N. Six new 3d-4f heterometallic coordination polymers constructed from pyrazole-bridged CuIILnIII dinuclear units. Dalton Trans. 2013, 42, 13997–14005; https://doi.org/10.1039/c3dt51015h.Search in Google Scholar PubMed

8. Branzea, D. G., Guerri, A., Fabelo, O., Ruiz-Pérez, C., Chamoreau, L.-M., Sangregorio, C., Caneschi, A., Andruh, M. Heterobinuclear complexes as tectons in designing coordination polymers. Cryst. Growth Des. 2008, 8, 941–949; https://doi.org/10.1021/cg700846x.Search in Google Scholar

9. Dou, Q.-Q., He, Y.-K., Zhang, L.-T., Han Z.–B. catena–Poly[4,4′-bipyridinium [bis(μ3-pyrazole-3,5-dicarboxylato-κ5O5,N1:N2,O3:O3) dicopper(II)]]. Acta Crystallogr. 2007, E63, m2908–m2909; https://doi.org/10.1107/s1600536807054864.Search in Google Scholar

10. Wang, L., Guo, B., Li, H.-X., Li, Q., Li, H.-Y., Lang, J.-P. Polynuclear copper(ii) pyrazolate complexes: temperature-dependent protonolysis reactions, crystal structures and high catalytic activity toward the condensation of nitriles with 2-aminoalcohol. Dalton Trans. 2013, 42, 15570–15580; https://doi.org/10.1039/c3dt51970h.Search in Google Scholar PubMed

11. Klongdee, F., Sasada, Y., Nakano, M., Chainok, K., Youngme, S., Synthesis, B. J. X-ray structures, and magnetic properties of seven polynuclear Cu(II) complexes containing pyrazole-3,5-dicarboxylate with various ancillary ligands. New J. Chem. 2023, 47, 9669–9680; https://doi.org/10.1039/d3nj00821e.Search in Google Scholar

Received: 2023-07-02
Accepted: 2023-08-20
Published Online: 2023-09-05
Published in Print: 2023-12-15

© 2023 the author(s), published by De Gruyter, Berlin/Boston

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

Articles in the same Issue

  1. Frontmatter
  2. New Crystal Structures
  3. Crystal structure of bis(dimethylammonium) poly[(μ4-1,1′-(1,4-phenylenebis(methylene))bis(1H-pyrazole-3,5-dicarboxylato))-κ6O1, N2:O2:O3:O1′,N2′]nickel (II)], C22H26N6NiO8
  4. Hydrothermal synthesis and crystal structure of catena-poly[diaqua-bis(μ2-4-((pyridin-4-ylmethyl)amino)benzoato-κ2N:O)cobalt(II)] 4,4′-bipyridine – water (1/2/2)
  5. Crystal structure of (2S,3S,4S,5S, Z)-2,3,5,6-tetrakis(benzyloxy)-4-hydroxyhexanal oxime, C34H37NO6
  6. The crystal structure of hexakis(3-thiophenecarboxylato-κ2O,O″)-bis(1,10-phenanthroline-κ2N,N′) trimanganese(II), C54H34N4O12S6Mn3
  7. Crystal structure of catena-poly[(μ2-1,4-di(pyridin-4-yl)benzene-κ2N:N′)-(4-bromobenzoate-κ2O:O′)-(μ-2-bromobenzoate-κ2O,O′)nickel(II)] – water (2/1), C30H21Br2N2NiO4.5
  8. The crystal structure of poly[(μ3-1,3-phenylenedioxydiacetate-κ5O,O,O′,O″,O‴)-bis(4′-(4-(1H-imidazol-1-yl)phenyl)-4,2′:6′,4″-terpyridine-kN) cadmium(II)], C58H42CdN10O6
  9. The crystal structure of 5-chloro-6′-methyl-3-(4-(methylsulfonyl)phenyl)-[2,3′-bipyridin]-1′-ium 4-methylbenzenesulfonate
  10. Crystal structure of poly[(μ-benzoato)-(μ-cis-4–hydroxy-D-proline)lithium], C12H14LiNO5
  11. The crystal structure of catena-poly[aqua-(4-iodopyridine-2,6-dicarboxylato-κ3N,O,O)-copper(II)] monohydrate, C7H6NO6ICu
  12. The crystal structure of catena-[diaqua-(4-acetylphenoxyacetato-κ2O,O)-bis(4-acetylphenoxyacetato-κ3O,O:O)-dihydrate-lanthanum(III)]–4,4′-bipyridine (2/1), C35H35NO14La
  13. The crystal structure of catena-poly[(4-iodopyridine-2,6-dicarboxylato-κ4 O,N,O′,O′′)(4-imidazol-1-yl-pyridine-κN)copper(II)], C15H9N4O4ICu
  14. Crystal structure of polybis(μ 4-3,5-dicarboxylatopyrazol-1-yl)-bis(N,N-dimethylformamide)tri-copper(II)–acetonitrile (1/2), C20H22Cu3N8O10
  15. Crystal structure of poly[(μ2-5-hydroxy-isophthalato-κ4O,O′:O″,O‴)-(μ2-1,5-bis(imidazol-2-methyl)pentane-κ2N:N′)cadmium(II)], C21H24CdN4O5
  16. The crystal structure of poly[bis(μ2-1,4-bi(1-imidazolyl)benzene-κ2N:N′)bis(μ2-4,4′-methylenebis(3-hydroxy-2-naphthoate)-κ2O:O′)cobalt(II)], C35H24CoN4O6
  17. The crystal structure of a cobalt-vanadium-oxido hydrate
  18. The crystal structure of catena-poly[(μ 2-2H-1,2,3-triazole-4,5-dicarboxylato-κ 2 O, O′)-(μ 2-1,3-bis((1H-imidazol-1-yl)methyl)benzene-κ 2 N,N′) zinc(II)], C18H15N7O4Zn
  19. Crystal structure of poly[diaqua-(bis(m2-1,4-bis(imidazol-1-ylmethyl)benzene)-κ2N,N′-manganese] dichloride, C28H32MnN8O2Cl2
  20. The crystal structure of 9,10-dimethoxy-5,6-dihydro-[1,3]dioxolo[4,5-g]isoquinolino [3,2-a]isoquinolin-7-ium (E)-3-(4-nitrophenyl)acrylate pentahydrate, C29H34N2O13
  21. Crystal structure of poly[(μ6-ammoniotris(methylene))tris(hydrogen phosphonato)cadmium(II)], C3H10CdNO9P3
  22. Crystal structure of Zn2[(1,1′-(hexane-1,6-diyl)bis(3-(pyridin-3-yl)urea))·(H2O)2·(DMF)2·(SO4)2], C24H50N8O18S2Zn2
  23. The crystal structure of 2-anilino-1,4-naphthoquinone, C10H11NO2
  24. Crystal structure of (E)-2-(2-(4-(diethylamino)styryl)-1-ethyl-1,4-dihydroquinolin-4-yl) malononitrile, C26H26N4
  25. Crystal structure of ethyl 2-((2,6-dichloro-4-(cyanomethyl)phenyl) amino)benzoate, C17H14Cl2N2O2
  26. Synthesis and crystal structure of 2-(3-oxo-3-phenylpropyl)isoindoline-1,3-dione, C17H13NO3
  27. The crystal structure of bis(acetonitrile-κ1N)tetrakis(μ2-2,6-difluorobenzoato-κ2O:O′)rhodium(II) (Rh–Rh), C32H18F8O8N2Rh2
  28. The crystal structure of a new polymorph of 6-hydroxy-2-naphthoic acid, C11H8O3
  29. The crystal structure of [(8-carboxymethoxy-quinoline-2-carboxylate-κ4N,O,O,O)-2,2′-bipyridine-κ2N-copper(II)] tetrahydrate, C22H23N3O9Cu
  30. The crystal structure of ethyl 4-hydroxy-2-(4-methoxyphenyl)-5-oxo-1-(2-oxo-2H-chromen-6-yl)-2,5-dihydro-1H-pyrrole-3-carboxylate, C23H19NO7
  31. Crystal structure of 7-hydroxy-3,4-dihydronaphthalen-1(2H)-one, C10H10O2
  32. Crystal structure of bis(tetrapropylammonium) dodecacarbonyltetratelluridotetraferrate(2-), (Pr4N)2[Fe4Te4(CO)12]
  33. The crystal structure of poly[bis(μ2−3−aminopyridine−4−carboxylatoκ2N:O)Zinc(II)], [Zn(C6H5N2O2)2] n
  34. The crystal structure of methyl 5-nitro-2-(tosyloxy)benzoate, C15H13NO7S
  35. The crystal structure of 18-crown-6 ― tetraaqua-dichlorido-di-μ2-chloridodicopper(II) (2/1), C12H32O10Cu2Cl4
  36. Crystal structure of 6,6a,7,8,9,10-hexahydro-5H-pyrazino [2,3-e]pyrido[1,2-a]pyrazine, C10H14N4
  37. Crystal structure of catena-poly-{diaqua-bis[μ-(((4-chlorophenyl)sulfonyl)glycinato-κO)](μ2-4, 4′-bipyridine-κ2N:N′)cobalt(II)} dihydrate, C26H30Cl2CoN4O12S2
  38. Crystal structure of bis{N′-[1,3-diphenylprop-2-en-1-ylidene]-N-phenylcarbamohydrazonothioato}zinc(II), C44H36N6S2Zn
  39. Crystal structure of tetraaqua-bis(((4-chlorophenyl)sulfonyl)glycinato-κO)cobalt(II) dihydrate, C16H26Cl2CoN2O14S2
  40. Crystal structure of 2-(5-phenyl-1-(quinolin-2-yl)-4,5-dihydro-1H-pyrazol-3-yl)phenol, C24H19N3O
  41. Crystal structure of 2-((2-fluoro-4-(trifluoromethyl)phenyl)(hydroxy)methyl)-7-methoxy-3,4-dihydronaphthalen-1((2H))-one, C19H16F4O3
  42. Crystal structure of 2-amino-4-(2-fluoro-3-(trifluoromethyl)phenyl)-9-methoxy-1,4,5,6-tetrahydrobenzo[h]quinazolin-3-ium chloride, C20H18ClF4N3O
  43. Crystal structure of (2-phenylimino methylquinoline-κ 2 N,N′)-bis(1–phenylpyrazole-κ 2 C,N)-iridium(III) hexafluorophosphate, C34H26F6IrN6P
  44. Crystal structure of (3-hydroxy-4-methoxyphenyl)(pyrrolidin-1-yl)methanone, C12H15NO3
  45. The crystal structure of bis(trimethylsulfoxonium) catena-poly[µ2-hexabromido-indium(III)sodium(I)] C6H18O2S2NaInBr6
  46. Crystal structure of N-cyclopropyl-3-hydroxy-4-methoxybenzamide, C11H13NO3
  47. The crystal structure of (bis(benzimidazol-2-yl-methyl)amine-κ3N,N,N )-(dihydrogen L-malate-κ2O,O )copper(II) perchlorate dihydrate, CuC20H24ClN5O12
  48. Crystal structure of (1E,1′E)-4,4′-(9,9-diethyl-9H-fluorene-2,7-diyl)dibenzaldehyde dioxime, C31H28N2O2
  49. Crystal structure of diethyl 1,9-bis(4-fluorophenyl)-4,6-diphenylhexahydro-3H-2,7,3,5-(epimethanetriyliminomethanetriyl)cyclopenta [b]pyridine-3,7(2H)-dicarboxylate, C40H36F2N2O4
  50. Crystal structure of bis(benzene-1 carboxylato-O 3,5-carboxyl-κ1O)-[(5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-κ4N,N′,N′′,N′′′)nickel(II) ─ benzene-1,3,5-tricarboxylic acid ─ water (1/2/4), C52H66N4NiO28
  51. Crystal structure of 1,4-dibromo-2,5-bis(2-methoxyethoxy)benzene-1,4-diol, C12H16Br2O4
  52. Crystal structure of dicarbonyl[N,N′-(1,2-dimethyl-1,2-ethanediylidene)bis[2,6-bis(1-methylethyl)benzenamine]-N,N′]nickel(0), C30H40N2NiO2
  53. Crystal structure of 1,4-dibromo-2,5-bis(prop-2-yn-1-yloxy)benzene, C12H8Br2O2
  54. Crystal structure of O-(3-(benzo[d]thiazol-2-yl)naphthalen-2-yl) O-phenyl carbonothioate, C24H15NO2S2
  55. The crystal structure of (E)-4-fluoro-N′-(1-(4-hydroxyphenyl)propylidene)benzohydrazide, C16H15FN2O2
  56. Crystal structure of (E)-1-(benzo[d]thiazol-2-yl)-N-(4,5-dihydropyren-2-yl)methanimine, C24H16N2S
  57. Crystal structure of 3-((4-bromophenyl)thio)-1H-indole, C14H10BrNS
  58. Synthesis and crystal structure of 1-((7-hydroxy-3-(4-hydroxy-3-nitrophenyl)-4-oxo-4H-chromen-8-yl)methyl)piperidin-1-ium-4-carboxylate monohydrate, C22H22N2O9
  59. Synthesis and crystal structure of (3E,5S,10S,13S,14S,17Z)-17-ethylidene-10,13-dimethylhexadecahydro-3H-cyclopenta[α]phenanthren-3-one O-(methacryloyl) oxime, C50H74N2O4
  60. Crystal structure of the hydrogen storage active phase La12Mg46LiMn
  61. The crystal structure of the salt: 4-((1,3-dioxoisoindolin-2-yl)carbamoyl)pyridine-1-ium 2-carboxybenzoate, C14H10N3O3·C8H5O4
  62. Crystal structure of (2-(2-pyridine)-benzimidazole-κ2 N,N′)-bis(1-phenylpyrazole-κ2 C,N)iridium(III) hexafluorophosphate, C30H22F6IrN7P
  63. Crystal structure of dichlorido-bis[2-(2,4-difluorophenyl)pyridine-κ1N]platinum(II), C22H14Cl2F4N2Pt
  64. Crystal structure of (5R,8R,9R,10R,12R,13R,14R, 17S,17Z)-2-((3-fluoropyridin-4-yl)methylene)-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, C36H52FNO3
Downloaded on 7.9.2025 from https://www.degruyterbrill.com/document/doi/10.1515/ncrs-2023-0308/html
Scroll to top button