Z. Kristallogr. NCS 2016; 231(2): 513–515
Open Access Alebel N. Belay*, Renier Koen, Johan A. Venter and Ruben M. Drost
Crystal structure of tris(N-nitroso-N-oxyanilinoκ2 O, O′) oxidoniobium(V), C18H15N6O7Nb Table 1: Data collection and handling. Crystal:
Red, cuboid, size 0.327×0.362×0.769 mm Mo K α radiation (0.71073 Å) 6.56 cm−1 Bruker APEX-II CCD, φ and ω scans 56° 35221, 4825 289 SHELX [29], Bruker software [30], Diamond [31], WinGX [32]
Wavelength: µ: Diffractometer, scan mode: 2θmax : N(hkl)measured , N(hkl)unique : N(param)refined : Programs:
DOI 10.1515/ncrs-2015-0172 Received July 31, 2015; accepted January 14, 2016; available online February 12, 2016
Abstract C18 H15 N6 O7 Nb, monoclinic, P21 /c (no. 14), a = 13.070(4) Å, b = 10.165(3) Å, c = 15.109(4) Å, β = 92.198(10)°, V= 2005.9(14) Å3 , Z = 4, Rgt (F) = 0.0318, wRref (F2 ) = 0.088, T = 100 K. CCDC no.: 1447423 The crystal structure is shown in the figure. Tables 1–3 contain details of the measurement method and a list of the atoms including atomic coordinates and displacement parameters.
Source of material Under atmospheric conditions, NbCl5 (0.27 g, 1 mmol) was dissolved in acetonitrile (10 mL), and treated with tetraethylammonium chloride (0.165 g, 1 mmol). The mixture was refluxed overnight at 90–100 °C and the solvent was removed under vacuum. The yellow Et4 N[NbCl6 ] was obtained. Dry Et4 N[NbCl6 ] (0.16 g, 0.56 mmol) was dissolved in absolute methanol (10 mL), and treated with cupferron *Corresponding author: Alebel N. Belay, Department of Chemistry, University of the Free State, Nelson Mandela Drive, Bloemfontein 9300, South Africa, e-mail:
[email protected] Renier Koen, Johan A. Venter and Ruben M. Drost: Department of Chemistry, University of the Free State, Bloemfontein 9300, South Africa
Table 2: Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2 ). Atom
Site
H(18) H(9) H(4) H(14) H(10) H(5) H(15) H(8) H(11) H(12) H(3) H(16) H(2) H(17) H(6)
4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e
x
y
z
Uiso
0.4415 0.8484 0.9605 0.6218 0.7542 0.9083 0.5214 0.8414 0.6523 0.6423 0.9763 0.3834 0.9445 0.3438 0.8669
0.4230 0.0346 −0.1836 0.2859 −0.1389 0.0301 0.3969 0.0822 −0.2631 −0.2150 −0.3319 0.5203 −0.2682 0.5341 0.0927
0.9488 1.4361 0.5523 0.7587 1.4904 0.5795 0.6523 1.2855 1.3943 1.2441 0.6675 0.6940 0.8112 0.8409 0.7214
0.037 0.032 0.031 0.026 0.032 0.031 0.032 0.027 0.037 0.031 0.031 0.039 0.028 0.044 0.026
(0.2604 g, 1.68 mmol) at room temperature. The resulting mixture was stirred for 4 h, and then the volatile material was removed in vacuo. The resulting residue was washed with diethyl ether (2 × 10 mL), giving a grey solid and the solution was left to stand at 255 K for a few days after which red crystals were obtained. The tetraethylammonium ion was not incorporated in the title compound. IR(KBr): vNbO 924.11 cm−1 . 1H NMR (300 MHz, CD3 OD): δppm = 6.54 (d, Ph-2H), 6.08 (m, Ph-13H). 13C NMR (300 MHz, CD3 OD): δppm = 131.20, 130.86, 130.79, 130.20, 130.06, 128.02, 127.12, 126.95, 118.08, 51.85, (Yield 0.165 g, 83.7%).
© 2016 Alebel N. Belay et al., published by De Gruyter. This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.
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514 | Belay et al.: C18 H15 N6 O7 Nb Table 3: Atomic displacement parameters (Å2 ). Atom
Site
Nb(1) O(7) O(4) O(6) O(5) O(1) O(3) O(2) N(5) N(6) N(1) N(2) N(3) C(1) C(7) C(18) C(13) C(9) C(4) N(4) C(14) C(10) C(5) C(15) C(8) C(11) C(12) C(3) C(16) C(2) C(17) C(6)
4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e 4e
x
y
z
U11
U22
U33
U12
U13
U23
0.78031(2) 0.8698(1) 0.6733(1) 0.6817(1) 0.6596(1) 0.8147(1) 0.7909(1) 0.8842(1) 0.6725(2) 0.7345(1) 0.9161(2) 0.8786(1) 0.6060(2) 0.9024(2) 0.7410(2) 0.4579(2) 0.5415(2) 0.8074(2) 0.9459(2) 0.5923(2) 0.5662(2) 0.7509(2) 0.9139(2) 0.5060(2) 0.8031(2) 0.6899(2) 0.6838(2) 0.9558(2) 0.4233(2) 0.9358(2) 0.3997(2) 0.8904(2)
0.12322(2) 0.2430(2) −0.0415(2) 0.2076(2) 0.2335(2) 0.0608(2) 0.0721(2) −0.0419(2) −0.0894(2) −0.0285(2) −0.0965(2) −0.0407(2) 0.2828(2) −0.0818(2) −0.0614(2) 0.4188(3) 0.3468(2) −0.0157(3) −0.1577(3) 0.2975(2) 0.3362(2) −0.1194(3) −0.0301(2) 0.4023(2) 0.0134(2) −0.1934(3) −0.1653(3) −0.2461(2) 0.4760(2) −0.2093(2) 0.4841(3) 0.0081(2)
0.99989(2) 1.0215(1) 1.0261(1) 0.9029(1) 1.0598(1) 0.8733(1) 1.1336(1) 1.0066(1) 1.1056(1) 1.1594(1) 0.9354(1) 0.8663(1) 0.9294(1) 0.7787(2) 1.2518(1) 0.8896(2) 0.8629(2) 1.3975(2) 0.6095(2) 1.0116(1) 0.7750(2) 1.4302(2) 0.6258(2) 0.7117(2) 1.3076(2) 1.3726(2) 1.2827(2) 0.6787(2) 0.7366(2) 0.7645(2) 0.8248(2) 0.7105(2)
0.0189(1) 0.0283(9) 0.0242(8) 0.0202(8) 0.034(1) 0.0234(8) 0.0243(8) 0.0248(8) 0.023(1) 0.0181(9) 0.023(1) 0.0164(9) 0.021(1) 0.014(1) 0.019(1) 0.026(1) 0.018(1) 0.027(1) 0.023(1) 0.031(1) 0.017(1) 0.027(1) 0.032(1) 0.023(1) 0.025(1) 0.032(1) 0.029(1) 0.027(1) 0.031(1) 0.026(1) 0.027(1) 0.025(1)
0.0157(1) 0.0206(8) 0.0256(8) 0.0197(8) 0.034(1) 0.0189(8) 0.0189(8) 0.0226(8) 0.025(1) 0.0163(9) 0.0198(9) 0.0156(8) 0.0188(9) 0.019(1) 0.021(1) 0.031(1) 0.016(1) 0.031(1) 0.033(1) 0.031(1) 0.019(1) 0.037(1) 0.028(1) 0.025(1) 0.023(1) 0.037(2) 0.028(1) 0.022(1) 0.021(1) 0.018(1) 0.030(1) 0.018(1)
0.0142(1) 0.0249(9) 0.0160(7) 0.0181(8) 0.0188(8) 0.0167(7) 0.0179(8) 0.0191(8) 0.0169(9) 0.0177(9) 0.020(1) 0.0197(9) 0.0206(9) 0.020(1) 0.016(1) 0.035(1) 0.029(1) 0.021(1) 0.021(1) 0.024(1) 0.029(1) 0.017(1) 0.018(1) 0.032(1) 0.021(1) 0.023(1) 0.020(1) 0.030(1) 0.043(2) 0.026(1) 0.052(2) 0.022(1)
0.00090(7) −0.0019(7) −0.0044(7) 0.0086(6) 0.0145(8) 0.0101(6) −0.0060(6) 0.0055(7) −0.0045(8) −0.0011(7) 0.0044(8) 0.0039(7) 0.0063(7) −0.0001(8) 0.0023(8) 0.011(1) 0.0037(8) −0.005(1) 0.002(1) 0.0117(9) −0.0007(8) −0.004(1) 0.002(1) −0.0066(9) −0.0030(9) −0.010(1) −0.007(1) 0.0059(9) 0.000(1) 0.0046(9) 0.014(1) 0.0033(9)
0.00005(7) −0.0024(7) −0.0018(6) 0.0012(6) 0.0029(7) 0.0001(6) −0.0015(6) −0.0008(6) 0.0001(7) 0.0010(7) −0.0009(8) 0.0003(7) 0.0020(7) −0.0007(8) 0.0019(8) −0.004(1) −0.0035(9) −0.0042(9) 0.0021(9) 0.0035(9) −0.0009(9) 0.0011(9) −0.0031(9) −0.004(1) 0.0004(9) −0.001(1) −0.0020(9) 0.004(1) −0.017(1) 0.0034(9) −0.012(1) −0.0034(9)
0.00035(7) 0.0021(7) 0.0001(6) −0.0016(6) −0.0003(7) 0.0005(6) 0.0018(6) 0.0025(6) −0.0011(8) 0.0009(7) 0.0016(8) −0.0004(7) −0.0029(7) −0.0034(9) 0.0010(8) −0.011(1) −0.0007(9) −0.002(1) −0.008(1) −0.0027(9) 0.0030(9) 0.004(1) 0.001(1) 0.006(1) 0.0019(9) 0.009(1) 0.002(1) −0.006(1) 0.002(1) 0.0009(9) −0.014(1) −0.0014(9)
Experimental details The H atoms were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C— H = 0.98 Å and Uiso(H) = 1.2Ueq(C), respectively. The highest peak (2.37 e. Å−3 ) is located 1.07 Å from O4 and the deepest hole (−0.65 e. Å−3 ) is situated 0.69 Å from Nb1.
oxido group. The cupferrate ligand forms a five- membered ring with a small bite angle (see the figure). The Nb—O distances are between 1.7107 (5) and 2.2267 (7) Å, and the O—Nb— O angles vary between 68.36(2)° and 158.51(2)°. All the bond distances and angles are similar to other relevant niobium(V) structures [27, 28].
Discussion
Acknowledgements: Financial assistance from the faculty
The ammonium salt of N-nitroso-N-phenylhydroxylamine, is a well-known analytical reagent (cupferron) and it was very popular especially for analytical separations [1, 2]. The chelate-forming derivatives of this ligand is known to form stable complexes with various metals, but only few of them have been structurally characterized [3–12]. Also some cupferrates were investigated in our group [13–18]. This study forms part of ongoing research to investigate the mechanism of the reactions of O,O′- and N,O-bidentate ligands with transition metals used in nuclear industry, such as Hf, Zr, Nb, Ta [19–26]. In the title structure the Nb atom is heptacoordinated by six oxygen atoms, of three bidentate cupferron ligands and an
of Natural and Agricultural science, Department of Chemistry, University of the Free State is gratefully acknowledged. Thanks are also due to Prof. Andreas Rooodt (head of the lab, Inorganic group), his financial support and helpful discussion.
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Belay et al.: C18 H15 N6 O7 Nb
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