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BY 4.0 license Open Access Published by De Gruyter (O) August 12, 2022

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

Yu Youzhu ORCID logo, Wang Hui, Li Leilei, Guo Yuhua, Fu Qianqian and Dai Jingtao

Abstract

C34H76N4O16Ti4, monoclinic, P21/n (no. 14), a = 10.0452(6) Å, b = 16.9053(8) Å, c = 14.6374(8) Å, β = 108.029(6)°, V = 2363.6(2) Å3, Z = 2, R gt (F) = 0.0678, wR ref (F 2) = 0.2126, T = 293(2) K.

CCDC no.: 2191522

The molecular 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: Colorless block
Size: 0.22 × 0.19 × 0.17 mm
Wavelength: Mo Kα radiation (0.71073 Å)
μ: 0.72 mm−1
Diffractometer, scan mode: Bruker APEX-II, φ and ω
θ max, completeness: 28.3°, >99%
N(hkl)measured, N(hkl)unique, R int: 42,194, 5844, 0.033
Criterion for I obs, N(hkl)gt: I obs > 2σ(I obs), 4680
N(param)refined: 268
Programs: Bruker [1, 2], Shelx [3], Diamond [4]

Table 2:

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

Atom x y z U iso*/U eq
C1 0.7522 (5) 0.8096 (3) 0.6315 (4) 0.0633 (11)
H1A 0.8121 0.8118 0.5908 0.076*
H1B 0.7353 0.7545 0.6426 0.076*
C2 0.8227 (5) 0.8490 (3) 0.7246 (4) 0.0685 (12)
H2A 0.7789 0.8322 0.7719 0.082*
H2B 0.9202 0.8330 0.7471 0.082*
C3 0.9167 (5) 0.9671 (3) 0.5910 (4) 0.0634 (11)
H3A 0.9754 1.0060 0.5732 0.076*
H3B 0.9434 0.9150 0.5753 0.076*
C4 0.9352 (5) 0.9725 (3) 0.6969 (4) 0.0690 (12)
H4A 1.0203 0.9454 0.7332 0.083*
H4B 0.9427 1.0275 0.7169 0.083*
C5 0.7848 (6) 0.9724 (4) 0.7984 (4) 0.0743 (13)
H5A 0.8120 1.0277 0.8038 0.089*
H5B 0.8369 0.9457 0.8572 0.089*
C6 0.6319 (6) 0.9650 (4) 0.7827 (4) 0.0768 (14)
H6A 0.6093 0.9113 0.7959 0.092*
H6B 0.6035 1.0004 0.8254 0.092*
C7 0.3244 (8) 0.8399 (5) 0.6210 (5) 0.100 (2)
H7A 0.3148 0.8945 0.6021 0.151*
H7B 0.4120 0.8323 0.6705 0.151*
H7C 0.2489 0.8253 0.6448 0.151*
C8 0.1849 (7) 0.8193 (4) 0.4692 (5) 0.0878 (15)
H8A 0.1076 0.7922 0.4820 0.105*
H8B 0.1738 0.8756 0.4778 0.105*
C9 0.1801 (5) 0.8049 (3) 0.3729 (4) 0.0666 (12)
H9A 0.1462 0.7515 0.3554 0.080*
H9B 0.1140 0.8412 0.3311 0.080*
C10 0.3233 (8) 0.7076 (4) 0.5518 (6) 0.0997 (17)
H10A 0.2534 0.6838 0.4975 0.120*
H10B 0.3000 0.6944 0.6095 0.120*
C11 0.4647 (6) 0.6745 (3) 0.5590 (5) 0.0754 (14)
H11A 0.5286 0.6835 0.6230 0.090*
H11B 0.4577 0.6179 0.5476 0.090*
C12 0.5563 (7) 0.8344 (5) 0.2160 (4) 0.094 (2)
H12A 0.5805 0.8660 0.1689 0.141*
H12B 0.4582 0.8400 0.2077 0.141*
H12C 0.5773 0.7799 0.2081 0.141*
C13 0.7905 (6) 0.8571 (5) 0.3361 (5) 0.101 (2)
H13A 0.8182 0.8033 0.3310 0.151*
H13B 0.8336 0.8757 0.4005 0.151*
H13C 0.8198 0.8896 0.2921 0.151*
C14 0.6376 (5) 0.8611 (4) 0.3129 (4) 0.0683 (13)
H14 0.6145 0.9171 0.3167 0.082*
C15 0.8642 (14) 0.6465 (8) 0.4449 (11) 0.191 (5)
H15A 0.9139 0.6564 0.5112 0.287*
H15B 0.8210 0.6946 0.4150 0.287*
H15C 0.9284 0.6278 0.4129 0.287*
C16 0.7642 (8) 0.5911 (5) 0.4384 (9) 0.134 (3)
H16 0.7661 0.5845 0.5054 0.161*
C17 0.7947 (12) 0.5112 (7) 0.4115 (11) 0.188 (5)
H17A 0.8841 0.5110 0.4004 0.282*
H17B 0.7234 0.4953 0.3540 0.282*
H17C 0.7967 0.4750 0.4625 0.282*
N1 0.3205 (4) 0.7919 (2) 0.5400 (3) 0.0515 (8)
N2 0.8144 (4) 0.9360 (2) 0.7153 (2) 0.0505 (8)
O1 0.5621 (3) 0.98428 (17) 0.68766 (19) 0.0504 (7)
O2 0.6237 (3) 0.84771 (15) 0.58526 (18) 0.0423 (6)
O3 0.4601 (2) 0.93255 (13) 0.47719 (17) 0.0369 (5)
O4 0.7749 (3) 0.98163 (17) 0.5407 (2) 0.0477 (6)
O5 0.5158 (3) 0.71102 (16) 0.4913 (2) 0.0547 (7)
O6 0.3088 (3) 0.81345 (17) 0.3580 (2) 0.0511 (7)
O7 0.5930 (3) 0.8220 (2) 0.3820 (2) 0.0578 (8)
O8 0.6369 (8) 0.6109 (7) 0.3958 (8) 0.281 (8)
H8 0.6180 0.6511 0.4206 0.422*
Ti1 0.61988 (6) 0.96734 (3) 0.58157 (4) 0.03438 (19)
Ti2 0.48102 (6) 0.81880 (4) 0.45464 (5) 0.03656 (19)

Source of material

All reagents and solvents employed in this work were commercially obtained and directly used without any purification.

Ti(OiPr)4 (6 mmol, 1.84 mL) was added with stirring to a mixture of N-methyldiethanolamine (H2MDEOA) (6.10 mmol, 0.70 mL) and triethanolamine (H3TEOA) (2.26 mmol, 0.30 mL). After 10 min, the resulting mixture was sealed in a Teflon-lined stainless vessel (15 mL) and heated at 353 K for 4 days under autogenous pressure. After cooling to room temperature, the above vessel was then further left at 273 K for 24 h, colorless block crystals were isolated and dried in air. Yield: 0.234 g (21%, based on triethanolamine).

Experimental details

All the non-H atoms were refined anisotropically. H atoms were subsequently treated as riding atoms with distances C–H = 0.96 (CH3), 0.97 (CH2) and 0.82 (OH) Å.

Comment

Titanium dioxide (TiO2) material is of significant importance which is widely investigated in photocatalysis field due to its high stability, negligible toxicity, and cheap cost [5]. The large band gap value (ca. 3.20 eV) of TiO2 greatly limited its applications because it can only absorb the ultraviolet region of solar radiation [6]. Doping TiO2 materials with nitrogen has been proved an effective approach to regulate their band gaps and strengthen efficiencies for their photocatalytic applications [7]. However, the imprecise and inhomogeneous characteristics of these nitrogen-doped TiO2 (N-TiO2) materials make it difficult to illustrate photocatalytic mechanisms clearly. To solve the above problem, nitrogen-doped titanium oxo clusters (N-TOCs) with accurate atomic structures have been used as the structure and reactivity models of N-TiO2 materials, which have attracted considerable attentions in the recent years [8, 9]. On the other hand, most N-TOCs characterized with N–Ti bond showed good photocatalytic performance such as photocatalytic degradation and H2 evolution [10, 11]. It is very necessary to enlarge the numbers and structure diversities of N-TOCs not only for investigation N-TiO2 materials but also for their future potential applications.

The flexibility of a ligand is critical for construction of a metal oxo compound. Flexible ligands are prone to construct clusters with unexpected structures because they can adopt a variety of conformations by freely rotation to meet the different coordination geometry of metal ions. H2MDEOA and H3TEOA belong to the flexible class of ligands and have been widely used for construction metal oxo clusters including N-TOCs [12], [13], [14], [15]. Combined utilization of H2MDEOA and H3TEOA to synthesize N-TOCs is desirable but rarely reported.

The title complex formulated as [Ti4(μ 3-O)2(MDEOA)2 (TEOA)2 (OiPr)2] ⋅ 2iPrOH belongs to the monoclinic system and the space group is P21/n. In the crystal structure, there are two Ti4+ ions, one μ 3-O, one MDEOA, one TEOA and one isopropoxide groups (the figure), and as well one solvent of iPrOH was observed in the asymmetric unit of the structrue. By an inversion center the tetranuclear target complex is generated (see the figure). All the Ti4+ ions show octahedral TiO5N coordination environments which were connected by two μ 3-O atoms and two μ 2-O atoms from ligands TEOA to generate the Ti4 core via edge-sharing mode. Intrestingly, the four Ti4+ ions are located in the same plane. Both the two MDEOA ligands adopt μ 1η 1:η 1:η 1 coordination mode, while the two TEOA present μ 2η 1:η 1:η 1:η 2 mode. The average bond lengths of Ti–N and Ti–μ 3-O are 2.3645 and 1.954 Å, respectively, corresponding to those in the literature [13], [14], [15].


Corresponding author: Yu Youzhu, School of Chemical and Environmental Engineering, Anyang Institute of Technology, Anyang 455000, Henan, P. R. China, E-mail:

Funding source: Anyang Institute of Technology

Award Identifier / Grant number: YPY2019003

Acknowledgments

This work was supported by the Foundation of Anyang Institute of Technology (YPY2019003).

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

  2. Research funding: Foundation of Anyang Institute of Technology (YPY2019003).

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

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Received: 2022-06-22
Accepted: 2022-07-20
Published Online: 2022-08-12
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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