Startseite Crystal structure of poly[diaqua-bis(μ 2-1,4-diaminobutane-N:N′)cobalt(II)] dichloride, C8H28Cl2CoN4O2
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Crystal structure of poly[diaqua-bis(μ 2-1,4-diaminobutane-N:N′)cobalt(II)] dichloride, C8H28Cl2CoN4O2

  • Shin Jiehye , Kang Jaeun und Junghwan Do ORCID logo EMAIL logo
Veröffentlicht/Copyright: 24. Februar 2023

Abstract

C8H28Cl2CoN4O2, orthorhombic, Fddd (no. 70), a = 10.116(2) Å, b = 13.532(3) Å, c = 23.507(5) Å, V = 3217.8(11) Å3, Z = 8, R gt (F) = 0.0361, wR ref (F 2) = 0.1069, T = 100.5 K.

CCDC no.: 2173635

A part of the title coordination polymer 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: Orange poly
Size: 0.09 × 0.07 × 0.07 mm
Wavelength: Synchrotron radiation (0.60997 Å)
μ: 0.91 mm−1
Diffractometer, scan mode: Rayonix MX225HS, ω
θ max, completeness: 29.9°, >99%
N(hkl)measured, N(hkl)unique, R int: 11425, 1837, 0.103
Criterion for I obs, N(hkl)gt: I obs > 2 σ(I obs), 1637
N(param)refined: 44
Programs: BL2D-SMC [1], Data processing [2], SHELX [3, 4], Diamond [5], Data collection [6]
Table 2:

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

Atom x y z U iso*/U eq
Co1 0.375000 0.375000 0.375000 0.00666 (9)
Cl1 0.625000 0.625000 0.43061 (2) 0.01384 (10)
O1W 0.375000 0.53230 (10) 0.375000 0.0159 (2)
H1 0.3206 (19) 0.5638 (15) 0.3642 (8) 0.024*
N1 0.52885 (8) 0.38060 (6) 0.44036 (4) 0.01040 (16)
H00E 0.573027 0.436918 0.435769 0.012*
H00F 0.488761 0.383971 0.474006 0.012*
C1 0.62708 (10) 0.29972 (10) 0.44334 (5) 0.0188 (2)
H00C 0.690223 0.308325 0.412686 0.023*
H00D 0.581855 0.237471 0.437046 0.023*
C2 0.70204 (10) 0.29329 (9) 0.49889 (4) 0.0175 (2)
H00A 0.639232 0.287023 0.529862 0.021*
H00B 0.750863 0.354196 0.504545 0.021*

Source of material

The mixture of CoCl2·6H2O (0.071 g, 0.3 mmol), 1,4-diaminobutane (0.090 mL, 0.9 mmol), muconic acid (0.043 g, 0.3 mmol) in ethanol (1.0 mL) was sealed under a vacuum in a Pyrex tube and heated to 70 °C for 68 h, then cooled to room temperature at 20 °C/h. The pH before and after the reaction were 8 and 7, respectively. The orange polyhedral crystals were recovered with unidentified light blue, violet, and white powder after vacuum filtration. The product is stable in air.

Experimental details

The data collection was carried out using synchrotron X-ray radiation on a Rayonix MX225HS CCD detector with a silicon(111) double-crystal monochromator at BL2D–SMC beamline of the Pohang Accelerator Laboratory, Korea. The PAL BL2D–SMDC program [1] was used for data collection, and HKL3000sm [2] was used for cell refinement, data integration, and absorption correction. The structure was solved using Direct Methods and refined by SHELXT and ShelxLe with the SHELXL plug-in [3, 4]. All hydrogen atoms bound to carbon and nitrogen atoms were placed in calculated positions and refined as riding model, and their positions and isotropic displacement parameters were refined.

Comment

The aliphatic diamine with two donor sites, 1,4-diaminobutane (dab) acts as a chelating agent in some cases, but it was mainly observed to act as a bridging ligand. The simple case where dab is used as a bridging ligand are the chain structures found in Cd(dab)X2 (X=Cl, Br), Hg(dab)Cl2 [7], and [Cd{SSi(OtBu)3}2(dab)(CH3OH)] n [8] in which the metal cation is coordinated by two bridging dab and two terminal ligands. Although very rare, there is an example that a metal cation is linked by four bridging dab to show an extending 2D polymeric structure, [Cu(dab)2(ClO4)2] n (H2O)2n [9]. In [Cu(dab)2(ClO4)2] n (H2O)2n , Cu(II) is equatorially coordinated by four N atoms from four dab. Two weakly bonded water molecules to Cu in trans–configuration complete an elongated octahedral geometry. Each of Cu(II) is in turn linked through dab, which extends to a 2D network with square-shaped voids.

Herein, we report a novel cobalt complex, Co(1,4–diaminobutane)2(H2O)·2Cl. To the best of our knowledge, this is the first 3D framework structure linked by the dab ligand. The crystal structure of the title compound is built of a 3D network with a diamonoid topology [10]. One crystallographically unique cobalt atom is coordinated with four nitrogen atoms from four symmetry related dab ligands (d(Co—N) = 2.1881(8) Å). The water molecules in trans–configuration (d(Co—O) = 2.2182(14) Å) complete the slightly distorted octahedral environment of Co1. The bond valence sum (BVS) calculation for Co gives a value of +2.18, indicating an oxidation state of +2 [11]. Each CoN4O2 octahedron is linked by four neighboring octahedra through dab ligands in a distorted tetrahedral geometry with the Co—Co—Co angles of 83.578(1)°, 109.446(1)° and 141.164(1)°, which extend to a diamond-type topological network, [Co(dab)2(H2O)2]2+. The framework contains distorted hexagonal-shaped 6-membered ring including the CoN4O2 octahedra. The {Co}6 rings intersect each other, forming crossing channels in the [011] direction. The hexagonal rings have wide and narrow regions; the shortest opposite C⃛C distance is 12.52 Å, and the longest is 15.3 Å. The chloride ions balance the framework charge and are located in the channels.


Corresponding author: Junghwan Do, Department of Chemistry, Konkuk University, Seoul 05029, Republic of Korea, E-mail:

Funding source: National Research Foundation of Korea (NRF)

Award Identifier / Grant number: 2021R1F1A1060277

Acknowledgments

J. Do thank the Pohang Accelerator Laboratory for beamline use (2022-2nd-2D-030).

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

  2. Research funding: This research was supported by the (NRF) grant funded by the Korea government (MSIT) (No. 2021R1F1A1060277).

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

References

1. Shin, J. W., Eom, K., Moon, J. BL2D–SMC, the supramolecular crystallography beamline at the Pohang Light Source II, Korea. J. Synchrotron Radiat. 2016, 23, 369–373; https://doi.org/10.1107/s1600577515021633.Suche in Google Scholar PubMed

2. Otwinowski, Z., Minor, W. Processing of X-ray diffraction data collected in oscillation mode. Methods Enzymol. 1997, 276, 307–326; https://doi.org/10.1016/s0076-6879(97)76066-x.Suche in Google Scholar

3. Sheldrick, G. M. A short history of SHELX. Acta Crystallogr. 2008, A64, 112–122; https://doi.org/10.1107/s0108767307043930.Suche in Google Scholar PubMed

4. Hübschle, C. B., Sheldrick, G. M., Dittrich, B. ShelXle: a Qt graphical user interface for SHELXL. J. Appl. Crystallogr. 2011, 44, 1281–1284.10.1107/S0021889811043202Suche in Google Scholar PubMed PubMed Central

5. Brandenburg, K. DIAMOND. Visual Crystal Structure Information System. Version 4.2.2; Crystal Impact: Bonn, Germany, 2016.Suche in Google Scholar

6. Arvai, A. J., Nielsen, C. ADSC Quantum-210 ADX Program; Area Detector System Corporation: Poway, CA, USA, 1983.Suche in Google Scholar

7. Ahuja, I. S., Singh, R. 1,3–propanediamine, 1,4-butanediamine (putrescine) and 1,5-pentanediamine (cadaverine) complexes with zinc(II), cadmium(II) and mercury(II) halides and pseudohalides. J. Coord. Chem. 1975, 4, 181–190; https://doi.org/10.1080/00958977508075897.Suche in Google Scholar

8. Pladzyk, A., Baranowska, K., Dziubińska, K., Ponikiewski, Ł. One dimensional coordination polymers generated from Cd(II) tri-tert-butoxysilanethiolates and flexible aliphatic diamines. Polyhedron 2013, 50, 121–130.10.1016/j.poly.2012.10.035Suche in Google Scholar

9. Du, J., Wei, G., He, J., Han, B., Dong, Z. [Cu(1,4–C4H12N2)2(ClO4)2]n(H2O)2n, a novel butane-1,4-diamine-bridged two-dimensional copper(II) square network: synthesis, structure, and magnetic properties. Mater. Lett. 2006, 60, 2248–2251; https://doi.org/10.1016/j.matlet.2005.12.125.Suche in Google Scholar

10. Zhang, H., Lin, P., Chen, E., Tan, Y., Wen, T., Aldalbahi, A., Alshehri, S. M., Yamauchi, Y., Du, S., Zhang, J. Encapsulation of an interpenetrated diamondoid inorganic building block in a metal-organic framework. Chem. Eur J. 2015, 21, 4931–4934; https://doi.org/10.1002/chem.201405710.Suche in Google Scholar PubMed

11. Brese, N. E., O’Keeffe, M. Bond-valence parameters for solids. Acta Crystallogr. 1991, B47, 192–197; https://doi.org/10.1107/s0108768190011041.Suche in Google Scholar

Received: 2022-05-02
Accepted: 2022-05-19
Published Online: 2023-02-24
Published in Print: 2023-06-27

© 2022 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. Crystal structure of phenyl(3,3-dichloro-1,3-dihydro-2H-pyrrolo[2,3-b]pyridin-2-one)methanone, C7H4Cl2N2O
  4. Crystal structure of poly[diaqua-bis(μ 2-1,4-diaminobutane-N:N′)cobalt(II)] dichloride, C8H28Cl2CoN4O2
  5. Synthesis and crystal structure of (4aR,7S)-7-hydroxy-7-isopropyl-1,1-dimethyldecahydro-2H,6H-8a,4a-(epoxymethano)phenanthren-12-one, C20H32O3
  6. The crystal structure of 1-(2-chlorobenzyl)-3-(3,5-dichlorophenyl)urea, C14H11Cl3N2O
  7. Crystal structure of tetrapropylammonium-1,3,5-thiadiazole-5-amido-2-carbamate – 1,2,4-thiadiazole-3,5-diamine – water (1/1/1), C17H37N9O3S2
  8. Tetrabutylammonium 1,3,5-thiadiazole-5-amido-2-carbamate—1,2,4-thiadiazole-3,5-diamine— water (1/1/1), C21H45N9O3S2
  9. The crystal structure of ((E)-2,4-dichloro-6-(((2-hydroxy-5-nitrophenyl)imino)methyl)phenolato-κ 3 N,O,O′)tris(pyridine-κN)manganese(II), C28H21Cl2MnN5O4
  10. The crystal structure of aqua-bis{2-bromo-6-((2-(2-phenylacetyl)hydrazineylidene)methyl)phenolato-κ3 N,O,O′}-dimethylformamide-κ1 O-erbium(III) chloride – dimethylformamide – water (1/2/1), C39H49N7O9Br2ClEr
  11. Crystal structure of (diaqua-bis(phenanthroline-K 2 N,N′)-tetrakis(m 2-3,4,5,6-tetrafluorophthalato-K 4 O,O:O′:O″;K 2 O:O′)dierbium (III) phenanthroline (1/2), C80H38Er2F16N8O18
  12. Crystal structure of (E)-7-methoxy-2-(4-methoxy-2-(trifluoromethyl)benzylidene)-3,4-dihydronaphthalen-1(2H)-one, C20H17F3O3
  13. The crystal structure of 4–(4,4,5,5–tetramethyl–1,3,2–dioxaborolan–2–yl)morpholine, C10H20BNO3
  14. The crystal structure of catena–poly[aqua(1-naphthoato-κ 2 O,O′)-(μ-1-naphthoato-κ 4 O:O,O′:O′)lead(II)], C22H16O5Pb
  15. The crystal structure of 1-(4-chlorophenyl)-3-cycloheptylurea, C14H19ClN2O
  16. The crystal structure of 4-(pyren-1-yl)butyl-4-nitrobenzoate, C27H21NO4
  17. Crystal structure of cyclo-(bis(µ2-3,3′-(1H-imidazole-3-ium-1,3-diyl)dipropionato-κ4 O,O′:O″,O″′)-dinitrato-κ2 O,O′-tetraoxido-diuranium(VI) C18H22N6O18U2
  18. The crystal structure of catena-[nitrato-κ 2 O,O′-(μ 3-3-iodobenzene-1,2-dicarboxylato-κ 4 O:O′:O″,O‴)-(2,2′:6′,2″-terpyridine-κ 3 N,N′,N″)lanthanum(III)], C23H14IN4O7La
  19. Redetermination of crystal structure of [bis(pyridin-2-ylmethyl)amine-κ 3 N,,]chloridopalladium(II) chloride monohydrate
  20. Crystal structure of catena-poly[triaqua-[bis(m2-4-(1H-1,2,4-triazol-1-yl)benzoato-k2O:O')-(4-(1H-1,2,4-triazol-1-yl)benzoato-k1O)-praseodymium (III) monohydrate], C27H26N9O10Pr
  21. Crystal structure of trans-diaqua-bis(methyl methylcarbamohydrazonothioato-κ2 N,N′) nickel(II) iodide semihydrate, C6H22N6O2NiS2I2·0.5H2O
  22. The crystal structure of 2-(2-fluoro-4-methyl-5-((2,2,2-trifluoroethyl)thio)phenyl)isoindolin-1-one, C17H13F4NOS
  23. The crystal structure of di-μ-1-naphthylacetato-κ 3 O,O′:O;κ 3 O:O,O′-bis[(1-naphthylacetato-κ 2 O,O′)(2,2′-bipyridine-κ 2 N,N′)lead(II)] monohydrate, C68H54N4O9Pb2
  24. Crystal structure of tetrapropylammonium guanidinium 4,4′-sulfonyldibenzoate monohydrate, C27H44N4O7S
  25. Crystal structure of bis(tetrapropylammonium) terephthalate – 1-(diaminomethylene)thiourea – water (1/2/4) C18H40N5O4S
  26. Crystal structure of (E)-7-fluoro-2-(4-morpholinobenzylidene)-3,4-dihydronaphthalen-1(2H)-one, C21H20FNO2
  27. The crystal structure of poly[diaqua-bis(μ 3-5-bromobenzene-1,3-dicarboxylato-κ 3 O,O,O′)-(μ 2-1,3-bis-(4-pyridyl)-propane-κ 2 N,N′)-dizinc(II))] – 5-bromobenzene-1,3-dicarboxylic acid [2/1], C37H29Br3N2O14Zn2
  28. The crystal structure of 2-bromo-1,3-phenylene bis(4-methylbenzenesulfonate), C20H17BrO6S2
  29. Crystal structure of europium dichromium icosaaluminum, EuCr2Al20
  30. The crystal structure of N1,N3-di((E)-benzylidene) isophthalohydrazide dihydrate, C 22 H 22 N 4 O 4
  31. Crystal structure of 7α,11α-dihydroxy-15-oxo-ent-kauran-16-en-19,6β-olide, C20H26O5
  32. Crystal structure of 4-chloro-N′-[(1E)-pyridin-3-ylmethylidene]benzohydrazide, C13H10ClN3O
  33. The crystal structure of (Z)-3-(1-(2-((E)-4-isopropylbenzylidene)hydrazinyl)ethylidene) chroman-2,4-dione, C21H20N2O3
  34. Crystal structure of E-7-fluoro-2-(2-(trifluoromethyl)benzylidene)-3,4-dihydronaphthalen-1(2H)-one, C18H12F4O
  35. Crystal structure of bis(6-aminopyridine-2-carboxylato–k2O,N)-bis(N,N-dimethylformamide-k1 O)zinc(II), C18H24N6O6Zn
  36. Crystal structure of 5-(adamantan-1-yl)-3-[(4-{[2-(trifluoromethyl)phenyl]-methyl}piperazin-1-yl)methyl]-1,3,4-oxadiazole-2(3H)-thione, C25H31F3N4OS
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