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Molecular structure of the functionalized bismuth alkoxide Bi[OC(CH2 NMe2)3]3

  • Gabriele Kociok-Köhn , Kieran C. Molloy EMAIL logo and Liam Palmer
Published/Copyright: July 10, 2014
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Main Group Metal Chemistry
From the journal Main Group Metal Chemistry Volume 37 Issue 3-4

Abstract

The molecular structure of the amino-functionalized bismuth alkoxide, Bi[OC(CH2 NMe2)3]3 has been determined and embodies a six-coordinate bismuth atom with a fac, fac-BiO3 N3 coordination sphere.

Keywords: alkoxide; bismuth; X-ray

Bismuth alkoxides are of importance as precursors for materials based on binary and ternary bismuth oxides (Mehring, 2007; Moniz et al., 2010, and references therein; Cosham et al., 2013). In such cases, either volatility and/or solubility are keys to precursor delivery; however, many Bi(OR)3 adopt either polymeric (Massiani et al., 1990, 1991; Matchett et al., 1990) or oligomeric structures (Jones et al., 1993; Boyle et al., 1998; Kessler et al., 2002; Hatanpaa et al., 2010). Attempts to reduce the nuclearity (and hence increase volatility, solubility) of these alkoxides have largely focused on the use of bulky alkoxide (Evans et al., 1989; Hanna et al., 2001; Brym et al., 2006; Kou et al., 2009; Hatanpaa et al., 2010) or siloxide ligands (Mansfeld et al., 2004; Paalasmaa et al., 2005), though the concomitant increase in molar mass and ligand complexity may not always result in benefits. The alternative use of functionalized alkoxide ligands, which can saturate the metal coordination sphere, have been much less well studied (Matchett et al., 1990; Herrmann et al., 1993; Williams et al., 2001). We now report the structure of Bi(tdmap)3 (1) [Htdmap=HOC(CH2 NMe2)3], which contains the highly functionalized tdmap ligand.

1 is monomeric and incorporates a six-coordinated BiN3 O3 environment, with the ligating atoms arranged in a fac-O3, fac-N3 manner (Figure 1). The three Bi-O bonds are of similar lengths [Bi-O(1) 2.113(5), Bi-O(2) 2.136(5), Bi-O(3) 2.140(5) Å], while one of the Bi-N bonds is elongated with respect to the other two [Bi-N(1) 2.721(6), Bi-N(4) 2.737(7), Bi-N(7) 2.879(6) A]. Although there is little regularity to the bond angles about bismuth resulting from the presence of three five-membered BiOC2 N rings, the largest angular distortions seem to involve the weakly coordinated N(7) [N(1)-Bi-N(7)113.07(18), N(4)-Bi-N(7)113.84(18)°] suggesting the presence of a stereochemically active lone electron pair in this vicinity, though this is by no means clear.

Figure 1 The asymmetric unit of 1 showing the labeling scheme used; thermal ellipsoids are at the 40% probability level.C(1) is hidden behind C(10); only key hydrogen atoms have been included for clarity. Selected geometric data: Bi-O(1) 2.113(5), Bi-O(2) 2.136(5), Bi-O(3) 2.140(5), Bi-N(1) 2.721(6), Bi-N(4) 2.737(7), Bi-N(7) 2.879(6) Å; O(1)-Bi-O(2) 90.93(19), O(1)-Bi-O(3) 88.75(19), O(1)-Bi-N(1) 69.44(19), O(1)-Bi-N(4) 84.16(19), O(1)-Bi-N(7)157.66(18), O(2)-Bi-O(3) 93.58(19), O(2)-Bi-N(1)159.6(2), O(2)-Bi-N(4) 71.86(19), O(2)-Bi-N(7) 82.91(18), O(3)-Bi-N(1) 80.87(19), O(3)-Bi-N(4)163.6(2), O(3)-Bi-N(7) 70.33(17), N(1)-Bi-N(4)110.13(19), N(1)-Bi-N(7)113.07(18), N(4)-Bi-N(7)113.84(18)°.
Figure 1

The asymmetric unit of 1 showing the labeling scheme used; thermal ellipsoids are at the 40% probability level.

C(1) is hidden behind C(10); only key hydrogen atoms have been included for clarity. Selected geometric data: Bi-O(1) 2.113(5), Bi-O(2) 2.136(5), Bi-O(3) 2.140(5), Bi-N(1) 2.721(6), Bi-N(4) 2.737(7), Bi-N(7) 2.879(6) Å; O(1)-Bi-O(2) 90.93(19), O(1)-Bi-O(3) 88.75(19), O(1)-Bi-N(1) 69.44(19), O(1)-Bi-N(4) 84.16(19), O(1)-Bi-N(7)157.66(18), O(2)-Bi-O(3) 93.58(19), O(2)-Bi-N(1)159.6(2), O(2)-Bi-N(4) 71.86(19), O(2)-Bi-N(7) 82.91(18), O(3)-Bi-N(1) 80.87(19), O(3)-Bi-N(4)163.6(2), O(3)-Bi-N(7) 70.33(17), N(1)-Bi-N(4)110.13(19), N(1)-Bi-N(7)113.07(18), N(4)-Bi-N(7)113.84(18)°.

Each tdmap is κ2-O,N bidentate, so the monomeric nature of 1 can be attributed to both N:→Bi coordination and the steric bulk of the ligand. We have observed similar low-nuclearity Group 12 complexes, e.g., [RM(tdmap)]2, M=Zn (Johnson et al., 2008a), Cd (Johnson et al., 2008b), where, again, tdmap uses only one of three available donor groups in metal coordination. Such a scenario does, however, leave several pendant donor groups available for further elaboration, which may be of significance in the synthesis of single-source precursors (SSPs) for ternary bismuth oxide materials. The orientation of the non-coordinating pendant CH2 NMe2 arms seems to be, at least in part, dictated by three weak intramolecular CH…O hydrogen bonds [H…O: 2.37–2.43 Å, C…O 2.98–3.07 Å, ∠C-H…O 120.4–122.1°; Figure 1], which are within the criteria used by others to identify such interactions [H…O<2.8 Å; ∠C-H…O>110°] (Desiraju, 1996).

The environmental differences between the three CH2 NMe2 groups are not, however, clearly evident in the 1H NMR spectrum, which show single resonances for the CH2 (albeit broad) and NMe2 groups. In the 13C NMR spectrum, some splitting of the signal due to the NMe2 groups is seen, while the CH2 signal again remains a singlet.

1 is soluble in common organic solvents and, as such, makes it amenable to use as a SSP in AACVD experiments. While we are yet to assess the volatility of this compound, previous experience with MeM(tdmap) (M=Zn, Cd) suggests it may have sufficient volatility for LPCVD use, but not APCVD (Johnson et al., 2008a,b).

Experimental

Htdmap (1.70 mL, 7.57 mmol) was added to Bi[N(SiMe3)2]3 (1.69 g, 2.44 mmol) in hexane (10 mL), causing a color change from yellow to dark orange. After heating at 65°C for 5 h, the solution was cooled to room temperature and then allowed to crystallize at -20°C. Yield 1.63 g, 81%. Analysis, found (calc. For C30 H72 N9 O3 Bi): C 44.1 (44.1), H 9.0 (8.9), N 14.8 (15.4)%. 1H NMR (d8-toluene): 2.32 (s, 18H, CH3), 2.66 (br s, 6H, CH2). 13C NMR (d8-toluene): 68.3 (OC), 68.3 (CH2), 46.7, 46.5 (CH3) ppm.

Crystallography

Experimental details relating to the single-crystal X-ray crystallographic study are summarized in Table 1. Data were collected on a Nonius Kappa CCD diffractometer (Enraf-Nonius B.V., Rotterdam, The Netherlands) at 150(2) K using Mo-Kα radiation (λ=0.71073 Å). Structure solution was followed by full-matrix least squares refinement and was performed using the WinGX-1.70 suite of programs (Farrugia, 1999). An absorption correction (semi-empirical from equivalents) was applied.

Table 1

Crystal data and structure refinement for 1.

1
Empirical formulaC30 H72 BiN9 O3
Formula weight815.95
Crystal systemTriclinic
Space group
a (Å)9.7454(3)
b (Å)9.8244(3)
c (Å)20.9747(4)
α (°)84.282(2)
β (°)83.852(2)
γ (°)84.881(1)
V(Å3)1980.42(9)
Z2
ρcalc (mg m-3)1.368
μ(Mo-kα) (mm-1)4.490
F(000)844
Crystal size (mm)0.33×0.33×0.20
Theta range (°)2.94–27.62
Reflections collected41113
Independent reflections [R(int)]9089 [0.1681]
Reflections observed (>2σ)7323
Data Completeness0.985
Max. and min. transmission0.4063, 0.2631
Goodness-of-fit on F21.051
Final R1, wR2 indices [I>2σ(I)]0.0608, 0.1453
R1, wR2 indices (all data)0.0833, 0.1591
Largest diff. peak, hole (eÅ3)2.694, -4.555

Supporting information

Crystallographic data for the structural analysis (in CIF format) has been deposited with the Cambridge Crystallographic Data Centre, CCDC no. 1002818. Copies of this information may be obtained from the Director, CCDC, 12 Union Road, Cambridge, CB21EZ, UK (Fax: +44-1233-336033; e-mail: deposit@ccdc.cam.ac.uk or www.ccdc.cam.ac.uk).

Corresponding author: Kieran C. Molloy, Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, UK, e-mail:

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Received: 2014-5-14
Accepted: 2014-6-18
Published Online: 2014-7-10
Published in Print: 2014-7-1

©2014 by De Gruyter

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https://doi.org/10.1515/mgmc-2014-0010
Keywords for this article
alkoxide; bismuth; X-ray
Creative Commons
BY-NC-ND 3.0

Articles in the same Issue

  1. Frontmatter
  2. Review
  3. Gallium compounds in nuclear medicine and oncology
  4. Research Articles
  5. Reaction of digermanes and related Ge-Si compounds with trifluoromethanesulfonic acid: synthesis of helpful building blocks for the preparation of Ge-Ge(Si)-catenated compounds
  6. Coordination propensity of N-protected amino acids and sterically congested heterocyclic β-diketones toward BuSnCl3: preparation and structural features of some new seven coordinated organic-inorganic hybrid formulations of monobutyltin(IV)
  7. The structures of strontium xanthates Sr(S2COR)2·xROH (R=Et, Pri, But)
  8. Synthesis, structural characterization and antibacterial activity of triorganotin ferrocenecarboxylates
  9. Short Communications
  10. Molecular structure of the functionalized bismuth alkoxide Bi[OC(CH2 NMe2)3]3
  11. Synthesis and crystal structure of Pb(II) complex with 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone
  12. [n-Bu2 NH2]3[SnPh3(SeO4)2]: the first triorganotin(IV) complex with terminally coordinated selenato ligands
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