Home Crystal structure of diaqua-diphenanthroline-κ2 N,N′-bis(μ2-2-carboxy-3,4,5,6-tetrafluorobenzoato-κ2 O:O′)-bis(μ2-tetrafluorophthalato-κ3 O,O′:O′)didysprosium(III) – phenanthroline (1/2), C80H38Dy2F16N8O18
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Crystal structure of diaqua-diphenanthroline-κ2 N,N′-bis(μ2-2-carboxy-3,4,5,6-tetrafluorobenzoato-κ2 O:O′)-bis(μ2-tetrafluorophthalato-κ3 O,O′:O′)didysprosium(III) – phenanthroline (1/2), C80H38Dy2F16N8O18

  • Xiao-Yu Zhang , Bei-Bei Zhao , Shi-Jie Huang , Jun-Ya Song and Xin-Fang Liu ORCID logo EMAIL logo
Published/Copyright: August 11, 2022

Abstract

C80H38Dy2F16N8O18, triclinic, P 1 (no. 2), a = 11.3924(5) Å, b = 12.7091(4) Å, c = 13.2583(5) Å, α = 102.496(3)°, β = 97.955(4)°, γ = 105.588(4)°, V = 1765.36(12) Å3, Z = 2, Rgt (F) = 0.0298, wRref (F 2) = 0.0606, T = 293(2) K.

CCDC no.: 2153477

The asymmetric unit of the title crystal 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: Colourless block
Size: 0.20 × 0.19 × 0.18 mm
Wavelength: Mo Kα radiation (0.71073 Å)
μ: 2.23 mm−1
Diffractometer, scan mode: SuperNova, ω
θ max, completeness: 29.3°, >99%
N(hkl)measured, N(hkl)unique, R int: 16224, 8196, 0.028
Criterion for I obs, N(hkl)gt: I obs > 2 σ(I obs), 7557
N(param)refined: 565
Programs: CrysAlisPRO [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
Dy1 0.41528 (2) 0.83634 (2) 0.44862 (2) 0.01792 (4)
F1 0.46272 (19) 0.80107 (17) 0.99306 (14) 0.0465 (5)
F2 0.70525 (19) 0.87111 (17) 1.08137 (14) 0.0451 (5)
F3 0.87048 (19) 1.00941 (19) 1.00099 (16) 0.0557 (6)
F4 0.79487 (18) 1.07260 (16) 0.83104 (14) 0.0428 (5)
F5 −0.06548 (18) 0.75199 (17) 0.43227 (16) 0.0489 (5)
F6 −0.17347 (19) 0.80968 (18) 0.26804 (16) 0.0525 (6)
F7 −0.04658 (19) 0.99209 (17) 0.20819 (14) 0.0434 (5)
F8 0.17727 (19) 1.12230 (16) 0.31852 (15) 0.0421 (5)
O1 0.3060 (2) 0.7478 (2) 0.78460 (19) 0.0479 (7)
O2 0.3239 (2) 0.9289 (2) 0.78652 (18) 0.0401 (6)
H2 0.2597 0.9024 0.7407 0.060*
O3 0.5768 (2) 1.07762 (16) 0.69644 (15) 0.0285 (5)
O4 0.49264 (19) 0.88821 (16) 0.63512 (14) 0.0238 (4)
O5 0.3519 (2) 1.17454 (16) 0.50476 (16) 0.0317 (5)
O6 0.38412 (18) 1.01348 (15) 0.51152 (14) 0.0210 (4)
O7 0.1425 (2) 0.8920 (2) 0.63637 (17) 0.0390 (6)
O8 0.24177 (19) 0.80514 (16) 0.52977 (15) 0.0258 (5)
O9 0.2311 (2) 0.7562 (2) 0.31571 (17) 0.0302 (5)
H9A 0.2473 0.7649 0.2553 0.045*
H9B 0.195 (4) 0.691 (4) 0.302 (3) 0.072 (15)*
N1 0.3704 (2) 0.63910 (19) 0.46976 (18) 0.0228 (5)
N2 0.4657 (2) 0.69544 (19) 0.30468 (18) 0.0240 (5)
C1 0.5001 (3) 0.8921 (2) 0.8576 (2) 0.0228 (6)
C2 0.5856 (3) 0.9620 (2) 0.8146 (2) 0.0233 (6)
C3 0.7076 (3) 1.0038 (3) 0.8668 (2) 0.0283 (7)
C4 0.7498 (3) 0.9734 (3) 0.9561 (2) 0.0325 (7)
C5 0.6662 (3) 0.9033 (3) 0.9967 (2) 0.0300 (7)
C6 0.5427 (3) 0.8659 (3) 0.9483 (2) 0.0275 (7)
C7 0.3651 (3) 0.8467 (3) 0.8053 (2) 0.0307 (7)
C8 0.5470 (3) 0.9779 (2) 0.7057 (2) 0.0214 (6)
C9 0.1800 (3) 1.0041 (2) 0.4349 (2) 0.0206 (6)
C10 0.1159 (3) 0.9065 (2) 0.4622 (2) 0.0220 (6)
C11 −0.0025 (3) 0.8454 (3) 0.4068 (2) 0.0295 (7)
C12 −0.0587 (3) 0.8733 (3) 0.3226 (2) 0.0317 (7)
C13 0.0038 (3) 0.9665 (3) 0.2934 (2) 0.0300 (7)
C14 0.1197 (3) 1.0325 (2) 0.3513 (2) 0.0262 (7)
C15 0.3120 (3) 1.0710 (2) 0.4878 (2) 0.0212 (6)
C16 0.1728 (3) 0.8648 (2) 0.5503 (2) 0.0236 (6)
C17 0.3245 (3) 0.6110 (3) 0.5504 (2) 0.0308 (7)
H17 0.3120 0.6672 0.6017 0.037*
C18 0.2941 (3) 0.5006 (3) 0.5618 (3) 0.0366 (8)
H18 0.2632 0.4849 0.6200 0.044*
C19 0.3099 (3) 0.4170 (3) 0.4879 (3) 0.0365 (8)
H19 0.2883 0.3431 0.4941 0.044*
C20 0.3815 (4) 0.3593 (3) 0.3211 (3) 0.0435 (9)
H20 0.3621 0.2845 0.3247 0.052*
C21 0.4299 (4) 0.3876 (3) 0.2411 (3) 0.0448 (9)
H21 0.4447 0.3323 0.1905 0.054*
C22 0.5141 (4) 0.5346 (3) 0.1501 (3) 0.0432 (9)
H22 0.5305 0.4817 0.0981 0.052*
C23 0.5430 (4) 0.6446 (3) 0.1480 (3) 0.0434 (9)
H23 0.5801 0.6679 0.0951 0.052*
C24 0.5165 (3) 0.7226 (3) 0.2259 (2) 0.0345 (8)
H24 0.5353 0.7974 0.2225 0.041*
C25 0.4382 (3) 0.5855 (2) 0.3080 (2) 0.0234 (6)
C26 0.4593 (3) 0.5008 (3) 0.2315 (2) 0.0323 (7)
C27 0.3590 (3) 0.4424 (2) 0.4016 (2) 0.0287 (7)
C28 0.3870 (3) 0.5553 (2) 0.3954 (2) 0.0238 (6)
N3 0.0923 (3) 0.5343 (2) 0.2690 (2) 0.0396 (7)
N4 0.1733 (3) 0.6083 (2) 0.1020 (2) 0.0408 (7)
C29 0.0460 (4) 0.4962 (4) 0.3450 (3) 0.0527 (10)
H29 0.0407 0.5487 0.4037 0.063*
C30 0.0049 (4) 0.3818 (4) 0.3422 (3) 0.0594 (12)
H30 −0.0292 0.3590 0.3967 0.071*
C31 0.0153 (4) 0.3045 (3) 0.2589 (3) 0.0549 (11)
H31 −0.0091 0.2279 0.2567 0.066*
C32 0.0724 (4) 0.2629 (3) 0.0846 (4) 0.0601 (12)
H32 0.0524 0.1862 0.0818 0.072*
C33 0.1095 (4) 0.2977 (3) 0.0027 (3) 0.0611 (12)
H33 0.1133 0.2448 −0.0564 0.073*
C34 0.1778 (4) 0.4554 (4) −0.0808 (3) 0.0575 (11)
H34 0.1797 0.4047 −0.1422 0.069*
C35 0.2082 (4) 0.5668 (4) −0.0744 (3) 0.0596 (12)
H35 0.2307 0.5939 −0.1310 0.071*
C36 0.2052 (4) 0.6407 (3) 0.0190 (3) 0.0520 (10)
H36 0.2272 0.7177 0.0230 0.062*
C37 0.1410 (3) 0.4959 (3) 0.0952 (3) 0.0348 (8)
C38 0.1433 (4) 0.4154 (3) 0.0046 (3) 0.0449 (9)
C39 0.0630 (3) 0.3401 (3) 0.1756 (3) 0.0428 (9)
C40 0.0989 (3) 0.4570 (3) 0.1827 (3) 0.0338 (7)

Source of materials

Dy(NO3)3·6H2O (0.0913 g, 0.2 mmol), 3,4,5,6-tetrafluorophthalate (0.054 g, 0.2 mmol) and phenanthroline (35.7 mg, 0.15 mmol) were mixed with 8 mL of deionized water in a reagent bottle. The mixture was treated by ultrasonic waves for 15 min at room temperature, sealed in a 25 mL Teflon-lined steel autoclave and heated at 110 °C for 72 h. The mixture was cooled to room temperature within 36 h and colorless block crystals were isolated after filtration, washed with distilled water and dried in air.

Experimental details

Using Olex2 [2], the structure was solved with the ShelXT [3] structure solution program and refined with the ShelXL [4] refinement package.

The carbon bound hydrogen atoms were placed in calculated positions and refined using a riding model on attached atoms.

Comment

In the last decades, a large number of Dy(III)-metal organic frameworks (MOFs) have been reported due to their excellent magnetic and optical properties [5], [6], [7]. Dy–MOFs can be constructed from Dy(III) ion and carboxylate and nitrogen-containing ligands [8], [9], [10]. Among various carboxylate ligands, tetrafluorophthalate (TFPA) is a good candidate because it has multiple coordinate modes and can serve as a bridging ligand [11], [12], [13]. In addition, phenanthroline (phen) is one of the commonly used N-containing ligands in combination with carboxylates [14, 15]. In this work, a binuclear Dy–complex was constructed with TFPA and phen as ligands. It is worth noting that, using the same reactants as described in the literature, different framework structures are produced due to different reaction conditions [9, 10]. Thus the dinuclear title complex was obtained unexpectedly.

In the title complex, there are one Dy(III) ion, one phen ligand, two differently deprotonated tetrafluorophthalato ligands (HTFPA and TFPA2−, respectively), one coordinated water and one cocrystallized phen in the asymmetric unit. The cocrystallized phen molecule is linked to the coordinated water by a hydrogen bond (O9–H9A⃛N3). Dy1 is nine-coordinated by two N atoms (N1, N2) of the phen ligand, one O atom (O9) from coordinated water, two O atoms (O4, O3A) from two mono-deprotonated HTFPA ligands and four O atoms (O6, O8, O5A and O6A) from two fully-deprotonated TFPA2− ligands. The Dy–N bond lengths are 2.506(2) and 2.561(2) Å and the Dy–O ones are in the range of 2.0560(14)–2.3610(19) Å. Two Dy(III) ions are bridged by two HTFPA and two TFPA2− ligands to form a dinuclear {Dy2} unit, which is further connected into a 3D structure by ππ interactions and C–H⃛O hydrogen bonds.


Corresponding author: Xin-Fang Liu, Henan Key Laboratory of Function–Oriented Porous Materials, College of Chemistry and Chemical Engineering, Luoyang Normal University, Luoyang, Henan 471934, P. R. China, E-mail:

Funding source: Training Program for Young Cadre Teachers of Higher Education Institutions in Henan Province

Award Identifier / Grant number: 2018GGJS128

Funding source: Science and Technology Development Project in Henan Province

Award Identifier / Grant number: 172101410037

  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 Training Program for Young Cadre Teachers of Higher Education Institutions in Henan Province (No. 2018GGJS128) and Science and Technology Development Project in Henan Province (No. 172101410037).

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

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Received: 2022-06-13
Accepted: 2022-06-13
Published Online: 2022-08-11
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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  43. Crystal structure of N 2,N 6-bis(2-(((E)-naphthalen-1-ylmethylene)amino)phenyl)pyridine-2,6-dicarboxamide, C41H29N5O2
  44. The crystal structure of 3-amino-1,2,4-triazolium 2,4,5-trinitroimidazolate, C5H5O6N9
  45. Hydrogen bonded dimers in the crystal structure of 2-chloro-N-(phenylcarbamoyl)nicotinamide, C26H20Cl2N6O4
  46. The crystal structure of 4,4′-bipyridine-5,6,7-trihydroxy-2-phenyl-4H-chromen-4-one-water(1/2/2), C40H32N2O12
  47. Crystal structure of N,N'-bis(4-fluoro-salicylaldehyde)-3,6-dioxa-1,8-diaminooctane, C20H22F2N2O4
  48. Crystal structure of 3-(1,3-dinitropropan-2-yl)-4H-chromen-4-one, C12H10N2O6
  49. The crystal structure of (4-(2-bromoethoxy)-phenyl)(phenyl)methanone, C15H13BrO2
  50. Crystal structure of (E)-7-bromo-2-(4-methoxybenzylidene)-3,4-dihydronaphthalen-1(2H)-one, C18H15BrO2
  51. Crystal structure of dichlorido-tetrakis((E)-(RS)-1-(2,4-dichlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-1-yl)pent-1-en-3-ol-κ 1 N)cadmium(II), C60H68O4N12Cl10Cd
  52. Crystal structure of diaqua-diphenanthroline-κ2 N,N′-bis(μ2-2-carboxy-3,4,5,6-tetrafluorobenzoato-κ2 O:O′)-bis(μ2-tetrafluorophthalato-κ3 O,O′:O′)didysprosium(III) – phenanthroline (1/2), C80H38Dy2F16N8O18
  53. Crystal structure of bis(μ2-2-oxido-2-phenylacetato-κ3 O,O′:O′)-bis(N-oxido-benzamide-κ2 O,O′)-bis(propan-2-olato-κ1 O)dititanium(IV), C36H38N2O12Ti2
  54. Crystal structure of poly[diaqua-(μ2-1H-benzo[d][1,2,3]triazole-5-carboxylato-κ2 O:O′)(μ2-oxalato-κ4O,O:O″,O′″)europium(III)] monohydrate, C9H10N3O9Eu
  55. Crystal structure of bis((N-methyl-2-oxyethyl)amine)-bis(μ 2-N,N,N-tris(2-oxoethyl)amine)-bis(isopropoxy)-bis(μ 3-oxo)tetratitanium(IV)– isopropanol (1/2), C34H76N4O16Ti4
  56. Synthesis and crystal structure of ethyl 4-((4-iodobenzyl)amino)benzoate, C16H16INO2
  57. Crystal structure of (Z)-2-(tert-butyl)-5-((5-(tert- butyl)-2H-pyrrol-2-ylidene)(mesityl)methyl)-1H-pyrrole, C26H34N2
  58. 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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