Abstract
C40H60Br2N4NiO8, triclinic, P1̄ (no. 2), a = 8.546(7) Å, b = 10.162(7) Å, c = 13.831(13) Å, α = 92.943(9)°, β = 101.096(8)°, γ = 111.710(5)°, V = 1085.1(15) Å3, Z = 1, Rgt(F) = 0.0317, wRref(F2) = 0.0905, T = 296(2) K.
The 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.
Source of material
An acetonitrile solution (20 mL) of [NiL](ClO4)2(0.270 g, 0.5 mmol) (L = trans-5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) was added to a solution of (2-(3-bromophenyl)-5-methyl-1,3-dioxane-5-carboxylic acid (0.301 g, 1.0 mmol) and NaOH (0.04 g, 1.0 mmol) in the minimum amount of water. Crystals of the title compound were obtained by slow evaporation within 5 days.
Data collection and handling.
| Crystal: | Blue block |
| Size: | 0.45 × 0.36 × 0.32 mm |
| Wavelength: | Mo Kα radiation (0.71073 Å) |
| μ: | 2.34 mm−1 |
| Diffractometer, scan mode: | Bruker APEX-II, φ and ω-scans |
| θmax, completeness: | 27.5°, >97% |
| N(hkl)measured, N(hkl)unique, Rint: | 12205, 4787, 0.023 |
| Criterion for Iobs, N(hkl)gt: | Iobs > 2 σ(Iobs), 3927 |
| N(param)refined: | 254 |
| Programs: | Bruker programs [1], SHELX [2], [3], DIAMOND [4] |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2).
| Atom | x | y | z | Uiso*/Ueq |
|---|---|---|---|---|
| Br1 | −0.21714(4) | 0.51494(3) | −0.06595(3) | 0.08254(13) |
| Ni1 | 0.5000 | 1.0000 | 0.5000 | 0.02777(9) |
| O1 | 0.2720(2) | 1.11420(16) | 0.20751(11) | 0.0475(4) |
| O2 | 0.35553(19) | 0.96579(16) | 0.11439(11) | 0.0468(3) |
| O3 | 0.7057(2) | 1.0292(2) | 0.30164(12) | 0.0586(4) |
| O4 | 0.55834(17) | 1.12103(14) | 0.38126(9) | 0.0370(3) |
| N1 | 0.3543(2) | 1.11582(16) | 0.52845(12) | 0.0325(3) |
| H1A | 0.3087 | 1.0815 | 0.5863 | 0.039* |
| N2 | 0.27779(19) | 0.86966(16) | 0.39373(11) | 0.0312(3) |
| H2A | 0.2954 | 0.9092 | 0.3317 | 0.037* |
| C1 | −0.1526(3) | 0.6824(3) | 0.02499(17) | 0.0514(5) |
| C2 | −0.2706(3) | 0.6935(3) | 0.07717(19) | 0.0553(6) |
| H29 | −0.3784 | 0.6196 | 0.0691 | 0.066* |
| C3 | −0.2248(3) | 0.8165(3) | 0.14139(18) | 0.0551(6) |
| H1 | −0.3033 | 0.8267 | 0.1763 | 0.066* |
| C4 | −0.0633(3) | 0.9250(3) | 0.15447(16) | 0.0501(5) |
| H2 | −0.0340 | 1.0076 | 0.1980 | 0.060* |
| C5 | 0.0556(3) | 0.9114(2) | 0.10290(15) | 0.0426(5) |
| C6 | 0.2325(3) | 1.0277(2) | 0.11624(15) | 0.0449(5) |
| H27 | 0.2324 | 1.0860 | 0.0620 | 0.054* |
| C7 | 0.4364(3) | 1.2304(2) | 0.22158(17) | 0.0508(5) |
| H26 | 0.4624 | 1.2868 | 0.2856 | 0.061* |
| H3 | 0.4311 | 1.2916 | 0.1705 | 0.061* |
| C8 | 0.5801(3) | 1.1777(2) | 0.21700(15) | 0.0440(5) |
| C9 | 0.5239(3) | 1.0748(3) | 0.12136(15) | 0.0515(6) |
| H5 | 0.5213 | 1.1270 | 0.0647 | 0.062* |
| H4 | 0.6068 | 1.0308 | 0.1200 | 0.062* |
| C10 | 0.6176(2) | 1.1013(2) | 0.30713(14) | 0.0363(4) |
| C11 | 0.2045(2) | 1.0693(2) | 0.44294(15) | 0.0388(4) |
| H25 | 0.2387 | 1.1147 | 0.3862 | 0.047* |
| H7 | 0.1142 | 1.0964 | 0.4592 | 0.047* |
| C12 | 0.1380(2) | 0.9081(2) | 0.41807(16) | 0.0394(4) |
| H8 | 0.1014 | 0.8627 | 0.4744 | 0.047* |
| H9 | 0.0392 | 0.8752 | 0.3619 | 0.047* |
| C13 | 0.2351(3) | 0.7130(2) | 0.36800(15) | 0.0369(4) |
| C14 | 0.5985(3) | 1.3052(2) | 0.64393(16) | 0.0415(5) |
| H11 | 0.5540 | 1.2456 | 0.6929 | 0.050* |
| H10 | 0.6313 | 1.4036 | 0.6723 | 0.050* |
| C15 | 0.4490(3) | 1.2724(2) | 0.55401(16) | 0.0403(4) |
| H16 | 0.4971 | 1.3095 | 0.4975 | 0.048* |
| C16 | 0.3318(3) | 1.3485(3) | 0.5744(3) | 0.0681(8) |
| H12 | 0.2363 | 1.3253 | 0.5182 | 0.102* |
| H13 | 0.3966 | 1.4499 | 0.5858 | 0.102* |
| H14 | 0.2890 | 1.3180 | 0.6322 | 0.102* |
| C17 | 0.1600(3) | 0.6286(2) | 0.44740(17) | 0.0474(5) |
| H17 | 0.2333 | 0.6728 | 0.5117 | 0.071* |
| H18 | 0.1529 | 0.5324 | 0.4356 | 0.071* |
| H19 | 0.0465 | 0.6274 | 0.4450 | 0.071* |
| C18 | 0.1050(3) | 0.6570(2) | 0.26785(17) | 0.0522(6) |
| H21 | 0.1530 | 0.7090 | 0.2174 | 0.078* |
| H20 | 0.0004 | 0.6694 | 0.2721 | 0.078* |
| H22 | 0.0798 | 0.5573 | 0.2511 | 0.078* |
| C19 | 0.0092(3) | 0.7884(3) | 0.03642(16) | 0.0472(5) |
| H28 | 0.0863 | 0.7780 | 0.0004 | 0.057* |
| C20 | 0.7490(4) | 1.3040(3) | 0.2165(2) | 0.0710(8) |
| H32 | 0.7829 | 1.3697 | 0.2764 | 0.107* |
| H30 | 0.7311 | 1.3520 | 0.1599 | 0.107* |
| H31 | 0.8382 | 1.2692 | 0.2130 | 0.107* |
Experimental details
The structure was solved using direct methods, which yielded the positions of all non-hydrogen atoms. These were refined first isotropically and then anisotropically. All the hydrogen atoms of the ligands were placed in calculated positions with fixed isotropic thermal parameters and included in the structure factor calculations in the final stage of full-matrix least-squares refinement. 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
Some metal compounds have attracted much attention owing to their widely application in fragrance and flavors and a protection of carbonyl or synthetic intermediate [5]. The title compound was synthesized by the reaction of (2-(3-bromophenyl)-5-methyl-1,3-dioxane-5-carboxylic acid with [NiL](ClO4)2. X-ray crystal structural analysis reveals that the asymmetric unit of the title structure contains one half of a cation [NiL]2+, and one anion [C12H12O4Br]−. The central Ni(II) atom displays a six-coordinate octahedral coordination geometry by coordination with four nitrogen atoms from L, and two oxygen atoms from (2-(3-bromophenyl)-5-methyl-1,3-dioxane-5-carboxylate. The Ni-N bond lengths [2.0777(18)–2.0942(19) Å] are slightly shorter than the Ni—O bond lengths [2.1277(18) Å]. The anion [ClO4]−, different from the similar structures [6], [7], has not been found in this title structure because the [Ni(trans-L)]2+ instead of [Ni(rac-L)]2+ was used to form this complex with two anionic and one neutral tetraaza ligand coordinated at Ni(II).
Acknowledgements
This work was financially supported by the Scientific Research Fund of Hunan University of Science and Engineering (16XKY064) and the construct program of applied characteristic discipline in Hunan University of Science and Engineering.
References
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©2019 Ying-Zhi Tan et al., published by De Gruyter, Berlin/Boston
This work is licensed under the Creative Commons Attribution 4.0 Public License.
