Home Physical Sciences Crystal structure and optical properties of diaqua-tris(nitrato-κ2O,O′)-bis(4,4,5,5-tetramethyl-2-(p-pyridyl)imidazoline-1-oxyl 3-oxide-κN)praseodymium(III), C24H36N9O15Pr
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Crystal structure and optical properties of diaqua-tris(nitrato-κ2O,O′)-bis(4,4,5,5-tetramethyl-2-(p-pyridyl)imidazoline-1-oxyl 3-oxide-κN)praseodymium(III), C24H36N9O15Pr

  • Dongjiao Li EMAIL logo , Zhiyuan Zhao , Xiuxiu Yao , Zhen Chen , Xiaoqiang Wu and Xiuwen Zheng
Published/Copyright: February 1, 2018

Abstract

C24H36N9O15Pr, monoclinic C2/c (no. 15), a = 23.686(9) Å, b = 11.727(5) Å, c = 12.001(5) Å, β = 94.852(4) V = 3322(2) Å3, Z = 4, Rgt(F) = 0.0282, wRref(F2) = 0.0769, T = 293 K.

CCDC no.:: 1812660

The crystal structure is shown in the figure. The asymmetric unit (one half of the title complex) is labelled. Tables 1 and 2 contain details on crystal structure and measurement conditions and a list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Dark brown
Size:0.48 × 0.32 × 0.10 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:1.55 mm−1
Diffractometer, scan mode:Bruker SMART APEXII, φ and ω-scans
θmax, completeness:28.1°, >99%
N(hkl)measured, N(hkl)unique, Rint:8654, 2929, 0.035
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 2752
N(param)refined:227
Programs:Bruker programs [5], SHELX [6]
Table 2:

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

AtomxyzUiso*/Ueq
Pr10.00000.387988(16)0.75000.02234(10)
O10.22952(11)0.1234(2)0.4062(2)0.0520(7)
O20.07327(8)0.2079(2)0.16470(16)0.0380(5)
O30.03829(10)0.1914(2)0.80485(19)0.0448(5)
O40.00000.0306(3)0.75000.0844(15)
O5−0.05333(9)0.4309(2)0.55991(17)0.0379(5)
O6−0.14382(10)0.4189(2)0.5145(2)0.0485(6)
O7−0.10924(11)0.3896(2)0.6848(2)0.0539(8)
O80.04304(10)0.5590(2)0.66919(17)0.0451(6)
H8A′0.04790.55230.60010.068*
H8B′0.05040.62420.69760.068*
N10.05945(9)0.3125(2)0.57979(18)0.0269(5)
N20.19659(10)0.1329(2)0.3172(2)0.0298(5)
N30.12093(9)0.1671(2)0.20370(18)0.0262(5)
N40.00000.1343(4)0.75000.0466(11)
N5−0.10418(11)0.4130(2)0.5847(2)0.0316(5)
C10.05844(12)0.2057(3)0.4093(2)0.0299(6)
H10.03790.16220.35510.036*
C20.03274(11)0.2490(3)0.4992(2)0.0293(6)
H2−0.00540.23300.50410.035*
C30.11454(12)0.3346(3)0.5701(2)0.0287(6)
H30.13380.37980.62450.034*
C40.14410(12)0.2942(3)0.4844(2)0.0285(6)
H40.18240.31060.48210.034*
C50.11562(11)0.2283(2)0.4013(2)0.0250(6)
C60.14423(11)0.1788(2)0.3095(2)0.0252(6)
C70.21400(13)0.0995(2)0.2032(3)0.0302(7)
C80.24811(15)0.1993(3)0.1633(3)0.0476(8)
H8A0.22420.26530.15420.071*
H8B0.26230.18030.09310.071*
H8C0.27930.21500.21760.071*
C90.24970(15)−0.0079(3)0.2126(3)0.0484(9)
H9A0.28550.00860.25290.073*
H9B0.2559−0.03500.13910.073*
H9C0.2303−0.06540.25170.073*
C100.15491(13)0.0863(3)0.1380(2)0.0304(6)
C110.15190(19)0.1214(3)0.0162(3)0.0507(10)
H11A0.11410.1101−0.01730.076*
H11B0.17780.0758−0.02220.076*
H11C0.16200.20040.01100.076*
C120.12868(14)−0.0311(3)0.1515(3)0.0487(8)
H12A0.1309−0.05100.22940.073*
H12B0.1489−0.08660.11160.073*
H12C0.0897−0.02980.12210.073*

Source of material

The educt 2-(4′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide (NIT4Py) was prepared by the literature method [1]. Pr(NO3)3⋅6H2O (0.046 g, 0.2 mmol) and NIT4Py (0.047 g, 0.2 mmol) were dissolved in 10 mL anhydrous THF. The mixture was stirred at room temperature for 4 h and then filtered. The dark brown filtrate was allowed to stand in the dark for 1 week. Dark brown crystals were obtained. Elemental analysis calculated (%) for C24H36N9O15 Pr: C, 34.66; H, 4.33; N, 15.52. Found (%): C, 34.47; H, 4.28; N, 15.42.

Experimental details

The hydrogen atoms were generated geometrically. The Uiso values of the hydrogen atoms of methyl groups were set to 1.5Ueq(C) and the Uiso values of all other hydrogen atoms were set to 1.2Ueq(C, N).

Discussion

In the complex [Pr(III)(NIT4Py)2(NO3)3(H2O)2], the Pr(III) is tenfold coordinated by three chelating nitrate anions, two aqua ligands and the pyridine nitrogens of two NIT4Py radical ligands. The water molecules occupy adjacent positions in the coordination polyhedron, and each is adjacent to a coordinating pyridine nitrogen. The coordinated Pr—N bond (2.726(2) Å) is longer than the coordinated Pr—O bond lengths (2.484(2)–2.639(3) Å). Only one pyridine nitrogen atom is coordinated in the radical and the oxygen atoms in the radical are uncoordinated. A hydrogen bond is formed between the coordinated water molecules O8 and nitronyl nitroxide O2 [x, 1 − y, 1/2 + z]. One further hydrogen bond is found between the water ligand O8 and O5 in a nitrate anion [−x, 1 − y, 1 − z]. Compared to the previous work [2], the location of nitronyl nitroxide in pyridyl ring is different. In the previous work, the nitrogen in pyridyl ring and the nitronyl nitroxide are in the ortho-position, thus they are both coordinated to the Pr(III) ion. In the pyroloxyl ligand, the distance of N(3)—O(2) and N(2)—O(1) is similar, and the distance of C(6)—N(3) and C(6)—N(2) is also similar. The similar distance indicates the pyroloxyl ligands contain a two-fold axis, which affects the coordination environment and symmetry of Pr in the complex.

The IR spectrum of the title complex presents two characteristic strong bands at 1302 cm−1 and 1448 cm−1, which can be attributed to the stretching vibrations of coordinated nitrate anions. The asymmetric stretching vibration band is near 1450 cm−1 and the symmetric stretching vibration bands is near 1300 cm−1. The difference of the two bands is near to 150 cm−1, indicating that the nitrate anions are coordinated in a bidentate fashion to the Pr(III) ion. The band of the N—O in NIT4Py can be clearly observed at 1368 cm−1, which indicates that N—O is uncoordinated to the Pr(III) ion [3]. The band at 3350 cm−1 is attributed to the O—H stretching vibration of the coordinated water molecules.

The optical properties of the complex and the free NIT4Py radical molecule were investigated at the excited wavelength 327 nm in tetrahydrofuran (THF) solution with the concentration 0.001 mol/L, respectively. The complex presents the similar emission peaks as that of a NIT4Py radical. But the optical intensity is enhanced and slightly red shifted. Similarly to the reported Pr(III) complex [4], optical enhancement and a slightly red-shift may be ascribed to the generation of H-bonding and the coordination between Pr(III) and nitrogen atom. The coordination may reduce the energy consumption from the atom vibrations. Our result reveals that the Pr(III) ion can significantly enhance the optical emission of the NIT4Py radical.

Acknowledgements

We acknowledge support from the National Natural Science Foundation of China (grant 21203086), Shandong Provincial Natural Science Foundation (grant ZR2012BL09), and the National Key Laboratory Fund for Shock Wave and Detonation Physics Research of the China Academy of Engineering Physics (grant 9140C671101110C6709).

References

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Received: 2017-5-16
Accepted: 2017-12-21
Published Online: 2018-2-1
Published in Print: 2018-3-28

©2018 Dongjiao Li et al., published by De Gruyter, Berlin/Boston

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 License.

Articles in the same Issue

  1. Cover and Frontmatter
  2. Crystal structure and optical properties of diaqua-tris(nitrato-κ2O,O′)-bis(4,4,5,5-tetramethyl-2-(p-pyridyl)imidazoline-1-oxyl 3-oxide-κN)praseodymium(III), C24H36N9O15Pr
  3. Crystal structure of dimethanol-bis(μ2-methanol-κ2O:O)-bis{3-((4-methoxy-2-oxidobenzylidene)amino)-2-oxo-2H-chromen-4-olato-κ3O,N,O′}dimanganese(II), C38H38Mn2N2O14
  4. Crystal structure of catena-poly[diaqua-bis(μ2-2-(2-((2,6-dichlorophenyl)amino)phenyl)acetato-κ3O,O′:O′)calcium(II)], C56H48N4Ca2Cl8O12
  5. Crystal structure of catena-poly[triaqua-(isophthalato-κO)-(μ2-1,6-di(1H-imidazol-1-yl)hexane-κ2N:N′)]nickel(II), C20H28N4NiO7
  6. Crystal structure of cyclo[hexaqua-bis[1-[(2-ethyl-1H-imidazol-1-yl) methyl]-1H-benzotriazole-κ2N:N′]-bis(sulfato-κ1O)dicadmium(II)] monohydrate, C24H42Cd2N10O16S2
  7. Crystal Structure of bis(2-fluorbenzoato-κO)-bis(1,10-phenanthroline-κ2N,N′)manganese(II) dihydrate, C38H28F2MnN4O6
  8. Crystal structure of tetrapropylammonium 5-hydroxyisophthalate tetrahydrate, C20H41NO9
  9. Crystal structural of 2-amino-4-(3-bromophenyl)-3-cyano-7,7-dimethyl-5-oxo-4H-5,6,7,8-tetrahydrobenzo[b]pyran, C18H17BrN2O2
  10. Crystal structural of 2-amino-4-(4-methoxyphenyl)-5-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitrile, C17H16N2O3
  11. Crystal structure of catena-poly[aqua(μ2-1,3-bis(1H-benzo[d]imidazol-1-yl)propane-κ2N:N′)-(μ2-5-(tert-butyl)isophthalate-κ3O,O′:O′′)nickel(II)], C29H30N4NiO5
  12. Crystal structure of catena-poly[(μ2-dicyanamido-κ2N:N′)-(μ2-2-(pyridin-2-yl)ethan-1-olato-κ3N,O:O′)copper(II)], C9H8CuN4O
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  14. The crystal structure of the formamide solvate of (17b)-estra-1,3,5(10)-triene-3,17diol, C19H27NO3
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  61. Crystal structure of {N-(3-ethoxy-2-oxidobenzylidene)-4-fluorobenzohydrazonato-κ3O,N,O′}dimethyltin(IV), C18H19FN2O3Sn
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