1. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.1 Radial distribution curve for electron diffraction by gaseous XeF 6. The continuous line represents the experimental curve, and the dashed line is theoretical curve calculated for a model with O h symmetry. Redrawn with permission from [1].Copyright 1968, American Institute of Physics.

2. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.2 Representations of deformation from O h symmetry consistent with electron diffraction data for gaseous XeF 6. The lone pair of electrons is shown to be repelling the fluorine atoms, to give structures with C 3v and C 2v symmetry. Redrawn with permission from [2]. Copyright 1968, American Institute of Physics.

3. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.3 NMR spectra for Xe 4 F 24. (a) 19 F NMR spectrum of a solution in O(SF 5 ) 2 at 155K and (b) 129 Xe NMR spectrum of a solution in SClFO 2 /CCl 2 F 2 at 128 K. (a) Adapted with permission [9]. Copyright 1974Wiley-VCH Verlag GmbH & Co.KGaA. (b) Redrawn with permission from [10]. Copyright 1978 American Chemical Society

4. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.4 Views of the polymeric xenon hexafluoride aggregates found in the cubic phase. Redrawn with permission from [11]. Copyright 1974 American Chemical Society. Xenon atoms are represented by small circles and bridging fluorine atoms by large circles. In (a) the tetramer is viewed with the4 axis parallel to [001], and in (b) the hexamer is shown with a 3-fold axis parallel to [111].

5. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.5 (a) EPR spectra of the green product formed from xenon with natural isotope abundance. It is best fitted by the following parameters: g  2.304; g || 1.855. A  ( 129 Xe) 22, ( 131 Xe) 6.52mT; A || ( 129 Xe) 60, ( 131 Xe) 17.8mT. (b) Spectrum obtained in the same way from xenon containing 80% 129 Xe; the patterns from the g  part of the spectrum are marked. Parts of spectra obtained with increased recorder gain are shown as insets. Redrawn from [12] and [13] with permission of The Royal Society of Chemistry. Copyright 1992 American Chemical Society.

6. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.6 UV/visible spectra of a solution of [XeF] + [Sb 2 F 11 ] – in SbF 5, before (yellow solution) and after to moistu (green solution). The positions of the lines used to excite the Raman spectra are marked. Redrawn from [12] and [13] with permission of The Royal Society of Chemistry. Copyright 1992 American Chemical Society.

7. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.7 (a) Raman spectrum, excited at 530.8 nm, of the green solution obtained when a solution of [XeF] + [Sb2F11] – in SbF 5 is exposed to moisture and held under a pressure of xenon. The band marked with an arrow is attributed to the product [Xe 2 ] +. (b) Raman spectrum of the same solution, excited at 676.4 nm. Redrawn from [14] with permission of The Royal Society of Chemistry.

8. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.8 Structure of the [Xe2] + cation beside a [Sb4F21] – anion in the crystal. Reprinted with permission from [15]. Copyright 1997 John Wiley & Sons.

9. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.9 UV/vis spectra of the cationic species [XeF] +,[Xe 2 ] + and [Xe 4 ] +. (b) Raman spectrum of the solution of the [Xe 4 ] + cation in Xe/SbF 5 solution. Reprinted with permission from [16]. Copyright 2007 John Wiley & Sons

10. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.10 The four proposed isomers of N 2 O 3 (a) asym, (b) sym (trans-trans), (c) trans-cis and (d) nitrosonium nitrite.

11. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.11 (a) The 1 and 3 bands of BiH 3. Lines marked * in the experimental spectrum (top) were attributed to residual H 2 O in the interferometer. (b) The 2 and 4 bands of BiH 3. Experimental (top) and simulated (bottom) spectra. The arrows in the simulated spectra (bottom) show the band centers. Reprinted with permission from [24]. Copyright 2002 John Wiley & Sons.

12. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.12 Part of the structure of [{Co(BH 4 ){Ph 2 P(CH 2 ) 5 PPh 2 } 2 ]0.5C 6 H 6. The phenyl groups and all hydrogen atoms bonded to carbon are omitted. Redrawn with permission from [26]. Copyright 1985 American Chemical Society.

13. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.13 NMR spectra of Al(BH 4 ) 3 : (a) 1 H spectrum, (b) 1 H spectrum with 27 Al decoupling, (c) 11 B spectrum and (d) 1 H spectrum with 11 B decoupling. Redrawn from [30] with permission of The Royal Society of Chemistry.

14. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.14 Mechanisms for exchange of terminal and bridge hydrogen atoms in Al(BH 4 ) 3. For clarity, only one BH 4 group is shown in detail.

15. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.15 Radial distribution curves for gaseous Be(BH 4 ) 2, obtained in separate experiments. Curve (a) is redrawn with permission from [32]. Copyright 1994 American Chemical Society. Curve (b) reprinted from [33] Copyright 1968 Acta Chem Scand./RSC. Note particularly the absence of a peak near 3.6 Å in curve (a).

16. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.16 Representation of the structure of crystalline Be(BH 4 ) 2. Half of the BH 4 groups (shown as tetrahedral) are linked by two hydrogen bridges to beryllium atoms (shown as circles). The remaining groups and the beryllium atoms are joined in helical polymers, each BH 4 being joined to two Be atoms by two pairs of hydrogen bridges. The figure shows one turn of a helix around a 4 1 axis. Redrawn with permission from [34]. Copyright 1972 American Chemical Society.

17. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.17 (a) 1 H and (b) 11 B NMR spectra of gaseous Be(BH 4 ) 2. The 11 B NMR spectrum shows coupling to four hydrogen nuclei, while the 1 H spectrum shows coupling to 11 B and to 10 B. The extra peak in the 1 H NMR spectrum is due to residual protons in deuteriated SiMe 4. Adapted with permission from [37]. Copyright 1978 American Chemical Society.

18. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.18 High-resolution synchrotron powder diffraction data: experimental data (dots), calculated for the refined structure (line), and allowed Bragg reflections (vertical bars) for Mg(BH 4 )2 2 NH 3. The lower trace shows the difference between the experimental data and those calculated for the refined structure. Reprinted with permission from [41]. Copyright 2008 American Chemical Society.

19. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.19 (a) Lateral view of the beryllocene molecule in the crystalline phase at low temperature, showing the two equivalent sites for the beryllium atom. Top views of the low-temperature (b) and room- temperature (c) structures show the change in the orientation of the rings with temperature. Adapted from [43]. Copyright 1984 CSIRO PUBLISHING.

20. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.20 Intramolecular rearrangement pathways of beryllocene, (a) gear-wheel mechanism and (b) molecular-inversion mechanism. Redrawn with permission from [49]. Copyright 1995, American Institute of Physics.

21. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.21 (a) 29 Si NMR spectrum of Ph 3 SiClO 4 with a resonance at 3 ppm. (b–d) 35 ClNMR spectra of (b) [Ph 3 C] + [ClO 4 ] – (0.125M in CH 2 Cl 2 /CH 3 CN), (c) covalently bonded Ph 3 Si-O-ClO 3, and (d) the solution of (c) hydrolyzed with three drops of H 2 O. (e) Molecular structure of Ph 3 SiClO 4 in the crystal. Reprinted with permission from [54]. Copyright 1987 American Chemical Society.

22. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.22 (a) Structure of the cation i PrSi–NCCH + 3, without the hydrogen atoms. Reprinted with permission from [55a]. Copyright 1998 American Chemical Society. (b) Structure of the salt Et 3 Si- [toluene] + [B(C 6 F 5 ) 4 ] –. Redrawn with permission from [56]. Copyright 1993Wiley-VCH Verlag GmbH & Co. KGaA. (c) Structure of the cation of (b) with a dashed interaction drawn between Si and a carbon atom of toluene. Reprinted with permission from [55c]. Copyright 1998 American Chemical Society.

23. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.23 Molecular structure of the cation [mes 3 Si] + [HCB 11 Me 5 Br 6 ] – ·(C 6 H 6 ).

24. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.24 IR spectra of (F 3 C) 2 POH and (F 3 C) 2 POD and their assignments. Redrawn with permission from [60]. Copyright 1962 American Chemical Society.

25. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.25 (a) Potential curve for (F 3 CF 2 C) 2 POH for variation of the dihedral angle C-P-O-H. (b) Temperature variation of the O — H stretching region of the IR spectrum of (F 3 CF 2 C) 2 POH. The high-frequency signal corresponds to the trans conformer; the low-frequency signal to cis. Adapted with permission from [61]. Copyright 2009 John Wiley & Sons.

26. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.26. Parts of the crystal structures of (a) (F 3 C) 2 POH and (b) (F 3 CF 2 C) 2 POH illustrating their aggregation into (a) chain polymers and (b) cyclic tetramers.

27. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.27. (a) 31 P NMR spectrum of the equilibrium mixture of the phosphinous acid [2,4- (F 3 C)2C 6 H 3 ] 2 POH and the phosphine oxide [2,4-(F 3 C) 2 C 6 H 3 ] 2 P(O)H; the inset on the right shows an expansion of the low-frequency signal. (b) 2D 31 P EXSY NMR spectrum of this equilibrium. Courtesy of Prof. Berthold Hoge, University of Bielefeld.

28. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.28. Orbital symmetries and electron donation/back-donation in transition-metal dihydrogen complexes.

29. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.29. Upon moving from a  acceptor (left) to a strong  donor (middle) to a weak s donor (right) the H — H bond length increases.

30. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.30. Classification of dihydrogen complexes based on the interatomic separation of H 2. Adapted with permission from [66]. Copyright 2007 American Chemical Society.

31. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.31. The ‘cis interaction’ between H 2 and a neighboring atom E (H, B, Si or C).

32. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.32. (a) Structure of the agostic titanium complex [TiCl 3 (dmpe)CH 2 CH 3 ]. Bond lengths are in Å, angles in degrees.(b)  -hydrogen elimination reaction. (c) and (d) Laplacian plots in the TiCCH plane, (c) based on an experimentally determined electron density distribution and (d) based on DFT calculations (B3LYP/AE-TZ//BPW91/AE-TZ). Adapted with permission from [73]. Copyright 2004 John Wiley & Sons.

33. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.33. (a) Constitution formula and (b) molecular structure of an agostic nickel complex with structural parameters (experimental [gray] and calculated [black, BP86/TZ2P]). Bond lengths are in Å, angles in degrees. (c) Laplacian of electron density in the NiCCH plane based on an experimentally determined electron density distribution. Adapted with permission from [74]. Copyright 2011 John Wiley & Sons.

34. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.34. (a) PES spectrum of P(NMe 2 ) 3. (b) Splitting of the orbital energy levels [N(2p) and P(3s)] by mutual (repulsive) interactions. Adapted with permission from [75]. Copyright 1973 American Chemical Society.

35. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.35. Two views of the crystal structure of P(NMe 2 ) 3.

36. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.36. (a) Gas-phase structure of Me 3 P=CH 2 determined by electron diffraction. (b) Structures and energies of three forms of Me 3 P=CH 2 : the free gas-phase molecule; as found in the solid state (crystal); and a calculated transition state for rotation of the CH 2 unit about the P=C axis. In each case there is a mirror plane, shown as a dashed line.

37. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.37. Molecular structures observed in the crystal of (a) the dimeric F 3 SiCH 2 NMe 2 and (b) the monomeric (F 5 C 6 )F 2 SiCH 2 NMe 2.

38. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.38. Molecular structures present in crystals of (a) F 3 SiN(SiMe 3 )NMe 2 and (b) F 3 SiNONMe 2.

39. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.39. (a) Difference (  ) between measured (C 6 D 6 solution) and calculated DFT-IGLO 1 H, 13 C, 15 N, 17 O, 19 F, and 29 Si NMR chemical shifts of F 3 SiONMe 2 as functions of the Si-O-N angle. (b) Determination of the equilibrium value of the Si····N distance of F 3 SiONMe 2 in C 6 D 6 solution by finding the minimum of the mean deviation of the moduli of all calculated NMR chemical shifts.

40. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.40. Radial distribution curve of ClH 2 SiONMe 2 as obtained from a gas-phase electron diffraction experiment. The experimental curve is drawn as solid line, and the fitted contributions of anti and gauche conformers are shown as dotted representations.

41. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.41. Electron density map of (F 3 C)F 2 SiONMe 2 in the plane of the SiON unit.

42. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.42. (a) EPR spectrum of [N(SF 5 ) 2 ] ●, showing an eleven-line multiplet, with the outermost lines clearly seen in the vertical expansion of the outer regions of the spectrum. (b) The theoretical pattern for coupling to ten equivalent spin-1/2 nuclei, (c) the theoretical intensity pattern for a 1:1:1 triplet of nonets, and (d) the difference between (b) and (c), on the same scale. Adapted with permission from [88]. Copyright 1986 American Chemical Society.

43. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.43. The structure of P 2 [CH(SiMe 3 ) 2 ] 4 in the crystalline phase. Redrawn from [91] with permission of The Royal Society of Chemistry.

44. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.44. Structures of half of Z 2[ CH(SiMe 3 ) 2 ] 4 (left) and {Z[CH(SiMe 3 ) 2 ] 2 } ● (right) (Z = P, As). In the radical the central C — H bonds (circled) are both directed inwards, allowing the bulky parts of the disyl groups to be further apart, reducing steric strain.

45. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.45. The connectivity of the low-temperature/pressure form of SQBP.

46. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.46. Comparison of form I (298 K, light grey) and form II (453 K, dark grey) SQBP. The calculation of the slipping angle was based on the intercept of the lines shown. Taken from [91] with permission of The Royal Society of Chemistry.

47. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.47. Comparison of the variable temperature X-ray diffraction (form I (298 K), form II (453 K)) and variable pressure powder neutron diffraction patterns. Note the peak intensities for the two different measurements are not comparable, but the peak positions are, as they depend solely on the unit cell dimensions. Reprinted with permission from [93]. Copyright 2009 American Chemical Society.

48. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.48. Representation of the porous structure of MOF-5, [Zn 4 O(bdc) 3 ] (bdc = 1,4- benzenedicarboxylate). The Zn 4 O(CO 2 ) 6 units are represented by tetrahedra, while the large sphere represents the largest available pore space in the crystal structure.

49. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.49. Percentage change in volume observed for MOF-5 in the presence of diethyl formamide pressure-transmitting medium (experimental data, filled squares) and MOF-5 without solvent (computational data, empty squares) as a function of pressure. Reprinted with permission from [95]. Copyright 2011 John Wiley & Sons.

50. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.50. ZIF-8 at (a) ambient pressure and (b) 1.47 GPa. Note the increase in size of the funnels surrounding the central nanopore. Reproduced with permission from [96]. Copyright 2009 Wiley-VCH Verlag GmbH & Co. KGaA.

51. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.51. The proposed preparation of Cu(I) and Ag(I) aryl complexes.

52. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.52. Crystallographic unit cell of the proposed Cu(I) and Ag(I) aryl complexes, determined by X-ray diffraction. The molecules are monomeric, with no signs of aggregation. Reproduced with permission from [98]. Copyright 1988Wiley- VCH Verlag GmbH & Co. KGaA.

53. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.53. Three possible forms of 12.VII (R = Cl) and 12.VIII (R = ligand described above) interpreted as (a) Pd(II)  Sn(II), (b) Pd(I)–Sn(III) and (c) Pd (0)  Sn(IV) complexes.

54. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.54. (a) Experimental 119 Sn MAS NMR spectrum of 12.VII recorded at spin = 14 kHz and (b) a simulated spectrum. Redrawn with permission from [101]. Copyright 2011 Wiley-VCH Verlag GmbH & Co. KGaA.

55. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.55. Experimental 119 Sn Mossbauer spectrum of 12.VII. Redrawn with permission from [101]. Copyright 2011Wiley-VCH Verlag GmbH & Co. KGaA.

56. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.56. Molecular structures of (a) [LFeCl] and (b) [LFe(µ-O)FeL]; hydrogen atoms are omitted for clarity. Courtesy of Prof Thorsten Glaser, University of Bielefeld.

57. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.57. Electronic absorption spectra of [LFe(µ-O)FeL], [LFeCl] and LH 2 as dichloromethane solutions. Courtesy of Prof Thorsten Glaser, University of Bielefeld.

58. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.58. Zero-field Mössbauer spectra of [LFeCl] and [LFe(µ-O)FeL] recorded at 80 K. Experimental data are provided by circles and simulations by lines. The intensities have been rescaled to visualize the differences in line widths and shapes. Courtesy of Prof Thorsten Glaser, University of Bielefeld.

59. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.59. (a) EXAFS data (solid lines) and fits to the data (dashed lines) for solid and frozen solution samples of [LFe(µ-O)FeL]. (b) Fourier transforms (without correction for phase shifts) of the data in (a) (from 2–11Å -1 ).

60. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.60. The structure of the first transition-metal complex that can reduce N 2 at atmospheric temperature and pressure. One of the hexa-iso-propylterphenyl (hipt) ligands is shown. Taken, with permission, from [109].

61. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.61. The catalytically active Fe 7 MoS 9 core of the FeMo cofactor, showing the location of the central ligand ‘X’. Adapted with permission from [112]. Copyright 2003 American Chemical Society.

62. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.62. Q-band 14 N ENDOR spectra of the regenerated resting state wild-type MoFe protein after turning over with 14 N showing four different N environments (labelled N1-N4). Adapted with permission from [112]. Copyright 2003 American Chemical Society.

63. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.63. The structure of the first synthetic Mn 4 Ca complex. Redrawn from [120] with permission of The Royal Society of Chemistry.

64. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.64. X-band EPR spectra of (a) C 60 without bombardment with nitrogen ions, (b) a sample bombarded with 15 N, and (c) a sample bombarded with nitrogen with its normal isotopic distribution, i.e. mainly 14 N. Reprinted from [125]. Copyright American Physical Society 1996.

65. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.65. Two views of the optimized structure of La 2 @ C 80, obtained by placing two lanthanum atoms inside the I h -symmetry form of C 80. Redrawn from [128]. Copyright 1995, with permission from Elsevier.

66. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.66. (a) A dysprosium atom encapsulated in C 82. (b) Fullerenes inserted in a carbon nanotube. (c) TEM image of Dy@C 82 inserted in a carbon nanotube. Reprinted with permission from [132]. Copyright 2010 John Wiley & Sons.

67. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.I. and 12.II

68. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.III (a, b, and c)

69. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.IV (a, b, and c)

70. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.V (a and b)

71. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.VI (a, b, c and d)

72. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.VII and VIII

73. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12.IX and X

74. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Discussion Problem Figure

75. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12. XI

76. Structural Methods in Molecular Inorganic Chemistry, First Edition. David W. H. Rankin, Norbert W. Mitzel and Carole A. Morrison @ 2013 John Wiley & Sons, Ltd. Published 2013 by John Wiley & Sons, Ltd. Figure 12. XII