Tris(2-Methoxyphenyl)Bismuthine Polymorphism Characterized by Nuclear Quadrupole Resonance Spectroscopy
Abstract
:1. Introduction
2. Materials and Methods
2.1. Sample Preparation
2.2. Sample Characterization
2.2.1. General
- determination of the peak transition frequencies and the full width at half maximum (FWHM) of the peaks for transition 7/2→5/2 of the Bi nucleus in all samples after reaching their final state
- observation of the evolution of the NQR spectrum during a certain time after shock freezing the melt of RM-SFLN
- the determination of the peak transition frequencies during a temperature sweep from 153 K to 325 K for the detection of potential phase transitions
- the determination of T2 relaxation times of CS and RM-SFW, partially at different temperatures
2.2.2. Experiment 1
2.2.3. Experiment 2
2.2.4. Experiment 3
2.2.5. Experiment 4
3. Results
3.1. Experiment 1
3.2. Experiment 2
3.3. Experiment 3
3.4. Experiment 4
3.5. X-ray Crystallography
4. Discussion
5. Conclusions
- Crystallization in the monoclinic space group P2(1)/c with only one molecule Tris(2-Methoxyphenyl)Bismuthine in the asymmetric unit
- Consequently, only a single 5/2-7/2 transition is observed at 88.75 MHz @310 K in contrast to the two transitions at 89.38 and 89.29 MHz for the trigonal polymorph which contains two crystallographically distinct molecules of Tris(2-methoxy-Phenyl)Bismuthine in the asymmetric unit.
- The NQR parameters Qcc and η of the new polymorph are 710.5 MHz and 0.05, respectively.
- Relaxometric data for the T2 time constant show a negative temperature coefficient for the new polymorph in contrast to a positive temperature coefficient (not very typical for the so far investigated Bi-Aryl-compounds [23]) of the reference polymorph in CS. This observation suggests clear differences in molecular dynamics.
- The NQR data of the new phase does not depend noticeably on the dynamics of freezing. The end products also show essentially the same FWHM at the same temperature, except for extremely fast freezing, which yields extremely broad (FWHM 1.8 MHz) peaks immediately after solidification. In the further time course, the peaks narrow considerably, even during storage at 77 K.
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
Appendix A
Empirical formula | C21 H21 Bi O3 | |
CCDC | 1941426 | |
Formula weight | 530.36 | |
Temperature | 100(2) K | |
Wavelength | 0.71073 Å | |
Crystal system | Monoclinic | |
Space group | P2(1)/c | |
Unit cell dimensions | a = 14.7365(5) Å | a = 90°. |
b = 7.9764(3) Å | b = 101.918(2)°. | |
c = 16.8250(6) Å | g = 90°. | |
Volume | 1935.05(12) Å3 | |
Z | 4 | |
Density (calculated) | 1.820 Mg/m3 | |
Absorption coefficient | 9.127 mm−1 | |
F(000) | 1016 | |
Crystal size | 0.250 × 0.170 × 0.130 mm3 | |
Theta range for data collection | 1.412 to 30.000°. | |
Index ranges | −20 ≤ h ≤ 20, −11 ≤ k ≤ 11, −23 ≤ l ≤ 23 | |
Absorption Correction | multi-scan/ SADABS | |
Reflections collected | 57633 | |
Independent reflections | 5575 [R(int) = 0.0693] | |
Completeness to theta = 30.000° | 98.8 % | |
Refinement method | Full-matrix least-squares on F2 | |
Data / restraints / parameters | 5575 / 0 / 229 | |
Goodness-of-fit on F2 | 1.072 | |
Final R indices [I > 2sigma(I)] | R1 = 0.0300, wR2 = 0.0848 | |
R indices (all data) | R1 = 0.0343, wR2 = 0.0912 | |
Extinction coefficient | n/a | |
Largest diff. peak and hole | 1.989 and -3.389 e.Å−3 |
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Temperature (K) | CS | RM-SFLN | RM-SFW | RM-S |
---|---|---|---|---|
310 | Site A: 89.384 Site B: 89.290 | 88.754 | 88.751 | 88.759 |
77 | not measurable | 90.713 | 90.710 | 90.704 |
Temperature (K) | CS | RM-SFLN | RM-SFW | RM-S |
---|---|---|---|---|
310 | Site A: 55.3 Site B: 55.6 | not measurable (poor SNR) | 50.1 | 51.2 |
77 | not measurable | 264 | 107.1 | 104.2 |
Time (min) | 26 | 46 | 89 | 1098 |
---|---|---|---|---|
FWHM (kHz) | 1844 | 808 | 375 | 264 |
95% conf. bounds | (826, 2863) | (189, 1427) | (219, 530) | (195, 333) |
Parameter | A | fT,0 | vQ3 | g@T0 |
---|---|---|---|---|
10−48 kg m2 | THz | MHz | 1/K | |
42.406 | 15.842 | 91.440 | 18.12 × 10−4 |
Title | CS Site A | CS Site B | RM-SFW |
---|---|---|---|
T2 @Transition 7/2 → 5/2 (μs) | 315 | 67 | 197 |
Space Group | P2(1)/c This work | Reference Site A [35] | Reference Site B [35] | |||
---|---|---|---|---|---|---|
Distances [Å] | Bi1-C1 | 2.247(3) | Bi1-C1 | 2.250(7) | Bi2-C22 | 2.248(7) |
Bi1-C8 | 2.250(2) | Bi1-C8 | 2.268(8) | |||
Bi1-C15 | 2.251(4) | Bi1-C15 | 2.260(10) | |||
Bi1-O1 | 3.106(5) | Bi1-O1 | 3.079(9) | Bi2-O4 | 3.097(9) | |
Bi1-O2 | 3.059(5) | Bi1-O2 | 3.117(9) | |||
Bi1-O3 | 3.140(5) | Bi1-O3 | 3.103(8) | |||
Angles [°] | C1-Bi1-C8 | 95.8(1) | C1-Bi1-C8 | 94.7(3) | C22-Bi-C22A | 93.5(4) |
C8-Bi1-C15 | 93.4(1) | C8-Bi1-C15 | 95.3(3) | |||
C1-Bi1-C15 | 93.1(1) | C1-Bi1-C15 | 92.6(3) |
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Scharfetter, H.; Fischer, R.; Krassnig, P.; Thonhofer, M.; Theyer, F.; Gösweiner, C. Tris(2-Methoxyphenyl)Bismuthine Polymorphism Characterized by Nuclear Quadrupole Resonance Spectroscopy. Crystals 2019, 9, 446. https://doi.org/10.3390/cryst9090446
Scharfetter H, Fischer R, Krassnig P, Thonhofer M, Theyer F, Gösweiner C. Tris(2-Methoxyphenyl)Bismuthine Polymorphism Characterized by Nuclear Quadrupole Resonance Spectroscopy. Crystals. 2019; 9(9):446. https://doi.org/10.3390/cryst9090446
Chicago/Turabian StyleScharfetter, Hermann, Roland Fischer, Paul Krassnig, Martin Thonhofer, Felix Theyer, and Christian Gösweiner. 2019. "Tris(2-Methoxyphenyl)Bismuthine Polymorphism Characterized by Nuclear Quadrupole Resonance Spectroscopy" Crystals 9, no. 9: 446. https://doi.org/10.3390/cryst9090446