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BY-NC-ND 3.0 license Open Access Published by De Gruyter (O) April 6, 2016

Crystal structure of (N,N′-bis(2-(((2,6-diisopropylphenyl)imino)methyl)phenyl)benzene-1,2-diamido-κ4O,O′,O′′,O′′′)oxidovanadium(IV), C44H48N4OV

  • Xiangdong Ji , Wei Gao and Ying Mu EMAIL logo

Abstract

C44H48N4O1V, triclinic, P1̅ (no. 2), a = 9.0540(10) Å, b = 10.5416(11) Å, c = 20.148(2) Å, α = 91.115(2)°, β = 95.150(2)°, γ = 99.630(2)°, V = 1887.1(4) Å3, Z = 2, Rgt(F) = 0.0618, wRref(F2) = 0.1553, T = 185 K.

CCDC no.:: 1425812

Tables 13 contain details of the methods used and a list of the atoms including atomic coordinates and displacement parameters.

Table 1:

Data collection and handling.

Crystal:Purple, block, size 0.12×0.15×0.17 mm
Wavelength:Mo Kα radiation (0.71073 Å)
μ:3.02 cm−1
Diffractometer, scan mode:CCD area detector, φ and ω scans
2θmax:50°
N(hkl)measured, N(hkl)unique:9280, 6505
Criterion for Iobs, N(hkl)gt:Iobs > 2 σ(Iobs), 5049
N(param)refined:459
Programs:BRUKER [13], SHELX [14]
Table 2:

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

AtomSitexyzUiso
H(42A)2i0.22761.25130.79530.057
H(42B)2i0.15391.36130.75780.057
H(42C)2i0.32721.35260.75220.057
H(19)2i0.05751.04250.59850.026
H(3)2i−0.16630.36520.73980.036
H(4)2i−0.19540.23940.64190.041
H(32)2i0.47031.03630.91810.042
H(20)2i−0.01530.79500.92130.030
H(28)2i−0.16130.98170.85350.031
H(14)2i−0.40560.67140.54710.033
H(15)2i−0.49010.80200.46780.036
H(40)2i0.47661.22800.70250.038
H(30)2i0.12861.23310.92450.035
H(6)2i−0.20780.55640.53340.037
H(17)2i−0.14651.08820.52570.031
H(43)2i0.07441.17270.69490.033
H(44A)2i0.29841.33610.62880.049
H(44B)2i0.12791.35720.63100.049
H(44C)2i0.16421.23540.59080.049
H(34A)2i0.11950.76390.58050.051
H(34B)2i0.14760.61890.58860.051
H(34C)2i0.28150.72860.57060.051
H(16)2i−0.36121.01100.45520.036
H(33)2i0.14850.71880.69460.031
H(31)2i0.38061.22120.94700.040
H(38)2i0.52560.85790.68500.036
H(11)2i−0.18660.65720.97070.041
H(39)2i0.62921.07430.69570.041
H(8)2i−0.37860.43490.77180.039
H(22)2i0.27740.77360.81730.039
H(35A)2i0.43270.65590.66720.058
H(35B)2i0.29210.55670.68830.058
H(35C)2i0.38130.66460.74090.058
H(5)2i−0.21800.33470.53890.043
H(9)2i−0.47800.37600.86960.049
H(10)2i−0.37510.48100.97110.053
H(29A)2i−0.14361.01600.96970.061
H(29B)2i−0.26721.09220.93520.061
H(29C)2i−0.10381.16830.96170.061
H(23A)2i0.34080.75340.95840.076
H(23B)2i0.34650.63900.90590.076
H(23C)2i0.19040.68640.91490.076
H(21A)2i0.52570.90380.82220.069
H(21B)2i0.52830.75490.83540.069
H(21C)2i0.55650.85770.89660.069
H(27A)2i−0.08401.25530.84500.061
H(27B)2i−0.24391.17150.81940.061
H(27C)2i−0.09801.15600.78270.061
Table 3:

Fractional coordinates and atomic displacement parameters (Å2).

AtomSitexyzU11U22U33U12U13U23
C(42)2i0.2267(5)1.3026(4)0.7552(2)0.046(2)0.029(2)0.037(2)−0.003(2)0.007(2)0.001(2)
V(1)2i−0.09442(6)0.80876(5)0.72933(2)0.0166(3)0.0192(3)0.0159(3)0.0000(2)−0.0003(2)0.0033(2)
N(1)2i0.0539(3)0.9306(2)0.6729(1)0.018(1)0.021(2)0.019(1)0.001(1)0.001(1)0.004(1)
N(3)2i−0.1545(3)0.6229(2)0.7517(1)0.026(2)0.017(2)0.019(1)0.000(1)−0.000(1)0.004(1)
O(1)2i−0.2181(2)0.8932(2)0.7428(1)0.023(1)0.032(1)0.025(1)0.007(1)−0.002(1)−0.000(1)
N(2)2i0.0141(3)0.8352(3)0.8310(1)0.017(1)0.024(2)0.018(1)0.002(1)−0.000(1)0.005(1)
N(4)2i−0.1699(3)0.7281(3)0.6384(1)0.021(2)0.023(2)0.018(1)−0.002(1)−0.002(1)0.003(1)
C(19)2i−0.0037(4)0.9732(3)0.6176(2)0.024(2)0.018(2)0.022(2)−0.000(1)0.005(1)0.004(1)
C(2)2i−0.1773(4)0.5355(3)0.6959(2)0.021(2)0.022(2)0.023(2)−0.002(1)0.004(1)0.002(1)
C(3)2i−0.1774(4)0.4043(3)0.6980(2)0.037(2)0.026(2)0.026(2)0.003(2)0.003(2)0.006(2)
C(4)2i−0.1933(4)0.3296(4)0.6399(2)0.043(2)0.020(2)0.039(2)0.003(2)0.008(2)0.001(2)
C(32)2i0.3668(4)1.0405(4)0.9079(2)0.016(2)0.051(3)0.032(2)−0.005(2)−0.004(2)0.003(2)
C(12)2i−0.1633(4)0.6538(3)0.8703(2)0.026(2)0.027(2)0.022(2)0.003(2)0.004(1)0.003(1)
C(24)2i0.2715(4)0.9347(3)0.8751(2)0.025(2)0.035(2)0.020(2)0.002(2)0.001(1)0.007(2)
C(13)2i−0.2233(3)0.8004(3)0.5888(2)0.022(2)0.026(2)0.015(2)0.002(1)0.001(1)0.004(1)
C(20)2i−0.0496(4)0.7662(3)0.8767(2)0.026(2)0.028(2)0.020(2)0.005(2)−0.002(1)−0.001(1)
C(26)2i0.0624(4)1.0549(3)0.8804(2)0.024(2)0.027(2)0.015(2)−0.001(1)−0.003(1)0.006(1)
C(28)2i−0.1040(4)1.0653(3)0.8732(2)0.026(2)0.027(2)0.024(2)0.005(2)−0.003(1)−0.000(1)
C(25)2i0.1194(4)0.9460(3)0.8609(2)0.027(2)0.026(2)0.013(2)−0.002(1)−0.001(1)0.006(1)
C(14)2i−0.3525(4)0.7565(3)0.5439(2)0.024(2)0.033(2)0.024(2)−0.002(2)0.000(1)−0.001(2)
C(15)2i−0.4019(4)0.8338(4)0.4964(2)0.021(2)0.047(2)0.021(2)0.004(2)−0.003(1)0.004(2)
C(40)2i0.4322(4)1.1398(3)0.6970(2)0.029(2)0.026(2)0.036(2)−0.007(2)−0.003(2)0.007(2)
C(30)2i0.1639(4)1.1570(3)0.9120(2)0.035(2)0.027(2)0.022(2)−0.001(2)0.000(2)0.001(2)
C(37)2i0.3064(4)0.8790(3)0.6831(2)0.025(2)0.024(2)0.018(2)0.002(1)−0.001(1)0.007(1)
C(41)2i0.2758(4)1.1060(3)0.6926(2)0.023(2)0.026(2)0.023(2)−0.001(1)−0.003(1)0.005(1)
C(36)2i0.2151(3)0.9747(3)0.6856(1)0.020(2)0.024(2)0.013(2)−0.002(1)−0.002(1)0.005(1)
C(6)2i−0.2022(4)0.5178(3)0.5756(2)0.037(2)0.033(2)0.019(2)−0.001(2)0.000(2)0.002(2)
C(17)2i−0.2000(4)1.0040(3)0.5310(2)0.028(2)0.027(2)0.024(2)0.005(2)0.003(1)0.005(1)
C(43)2i0.1821(4)1.2134(3)0.6937(2)0.029(2)0.021(2)0.032(2)0.001(2)0.004(2)0.003(2)
C(7)2i−0.2159(4)0.5847(3)0.8097(2)0.025(2)0.019(2)0.023(2)0.002(1)0.002(1)0.008(1)
C(44)2i0.1943(4)1.2928(3)0.6303(2)0.037(2)0.024(2)0.037(2)0.004(2)0.003(2)0.005(2)
C(18)2i−0.1479(3)0.9282(3)0.5822(2)0.019(2)0.024(2)0.017(2)0.005(1)0.002(1)0.005(1)
C(1)2i−0.1900(4)0.5941(3)0.6339(2)0.018(2)0.023(2)0.027(2)−0.002(1)−0.000(1)0.002(1)
C(34)2i0.1930(4)0.7098(4)0.5958(2)0.038(2)0.032(2)0.031(2)0.005(2)0.001(2)−0.005(2)
C(16)2i−0.3261(4)0.9586(4)0.4889(2)0.027(2)0.042(2)0.022(2)0.013(2)−0.002(1)0.009(2)
C(33)2i0.2407(4)0.7380(3)0.6702(2)0.029(2)0.023(2)0.026(2)0.003(2)0.003(1)0.004(2)
C(31)2i0.3137(4)1.1502(4)0.9255(2)0.035(2)0.031(2)0.027(2)−0.012(2)−0.003(2)0.001(2)
C(38)2i0.4611(4)0.9201(4)0.6870(2)0.023(2)0.037(2)0.031(2)0.010(2)0.002(2)0.010(2)
C(11)2i−0.2249(4)0.6120(4)0.9299(2)0.043(2)0.034(2)0.022(2)−0.003(2)0.005(2)0.006(2)
C(39)2i0.5231(4)1.0487(4)0.6936(2)0.018(2)0.037(2)0.046(2)−0.000(2)−0.003(2)0.010(2)
C(8)2i−0.3371(4)0.4809(4)0.8120(2)0.031(2)0.033(2)0.031(2)−0.003(2)0.003(2)−0.001(2)
C(22)2i0.3310(4)0.8126(4)0.8603(2)0.026(2)0.045(2)0.026(2)0.006(2)−0.002(2)0.000(2)
C(35)2i0.3462(4)0.6455(4)0.6938(2)0.046(2)0.028(2)0.041(2)0.010(2)−0.003(2)0.003(2)
C(5)2i−0.2063(4)0.3863(4)0.5789(2)0.043(2)0.032(2)0.029(2)−0.001(2)0.001(2)−0.006(2)
C(9)2i−0.3959(4)0.4453(4)0.8702(2)0.038(2)0.038(2)0.041(2)−0.012(2)0.010(2)0.006(2)
C(10)2i−0.3373(5)0.5090(4)0.9304(2)0.052(3)0.046(3)0.032(2)−0.006(2)0.016(2)0.012(2)
C(29)2i−0.1596(4)1.0874(4)0.9410(2)0.028(2)0.062(3)0.031(2)0.005(2)0.004(2)−0.005(2)
C(23)2i0.2993(5)0.7139(4)0.9148(2)0.045(3)0.058(3)0.054(3)0.023(2)0.006(2)0.013(2)
C(21)2i0.5008(4)0.8342(5)0.8530(2)0.027(2)0.075(3)0.038(2)0.016(2)−0.001(2)−0.002(2)
C(27)2i−0.1353(4)1.1716(4)0.8258(2)0.039(2)0.043(3)0.040(2)0.011(2)−0.002(2)0.009(2)

Source of material

The tetra-azane ligand (LH2) was synthesized according to the reported procedure [12]. The ligand LH2 (641 mg, 1.00 mmol) was dissolved in the mixed solvent of THF (20 mL) at 195 K, then a solution of n-BuLi (2.00 M in hexane, 1.00 mL, 2.00 mmol) was added dropwise to a solution of LH2. The mixture was allowed to warm to room temperature and stirred for 1 h, and then a slurry of VOCl2 (137.8 mg, 1.00 mmol) in THF (10 mL) was added. The solution was stirred at room temperature for 12 h. Then the volatiles were removed under reduced pressure and the residue was extracted into toluene. The product (Yield: 476 mg, 68.1%) was obtained as a purple powder after evaporating the solvent and washing with hexane. Dissolving the purple powder in CH2Cl2/hexane yielded a deep purple solution and after keeping the solution at 253 K for a period of three weeks, purple block-shaped crystals of the title compound were obtained.

Experimental details

All H atoms were placed in calculated positions and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.2Ueq(C).

Discussion

Over recent years vanadium complexes carrying different tetradentate ligands have been extensively investigated. Investigations into vanadium complexes are motivated by their wide range of properties useful for various applications, including pharmaceutics, catalysts and physiology [16]. The title compound is a very important organic intermediate in the applications of medicines [7]. The title structure VL crystallized with one V(IV) atom, one oxygen atom and a L ligand molecule in the asymmetric unit. The V(IV) centre atom is tetragonal-pyramidal coordinated by four nitrogen atoms from L and one oxygen atom (figure). The bond length between V1 and O1 (1.580(2) Å) is typical for five-coordinate vanadyl species, which is found in other V = O containing complexe [8]. The o-phenylenediamine groups with the two amine nitrogen atoms (N3, N4) are bonded to the V atom with a distance of 2.015(3) Å and 2.016(3) Å, respectively, which are shorter than that of V1—N1 (2.122(2) Å) and V1—N2 (2.182(3) Å), and each of them is in the common range [9, 10]. The angles between N2—V1—N3 (85.75(10)°), and for N1—V1—N4 (82.09(10)°) are in accordance with the bite angles found for a similar vanadium complex with the tetradentate ligand [11]. In the structure, the angle N2—V1—N4 is 160.88(11)°, and the apical position is occupied by the oxygen atom. The N2—V1—N4 is divided into two similar angles through V = O, N2—CV1—CO1 of 94.09(11)° and N4—CV1—CO1 of 102.25(11)°. Accordingly the following angles are: N1—CV1—CN3 = 142.00(11)°, N3—CV1—CO1 = 112.85(12)° and N1—CV1—CO1 = 103.14(11)°.

Acknowledgements:

This work was supported by the National Nature Science Foundation of China (21274050 and U1462111).

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Received: 2016-2-5
Accepted: 2016-3-16
Published Online: 2016-4-6
Published in Print: 2016-9-1

©2016 Xiangdong Ji et al., published by De Gruyter.

This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 3.0 License.

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