Supporting Information

Supporting Information for Gold(I) Alkynyls Supported by Mono- and Bidentate NHC Ligands: Luminescence and Isolation of Unprecedented Ionic Complexes Alexander A. Penney, Galina L. Starova, Elena V. Grachova, Vladimir V. Sizov, Mikhail A. Kinzhalov, and Sergey P. Tunik* Saint Petersburg State University, Institute of Chemistry, Saint Petersburg, Universitetsky pr. 26, 198504, Russian Federation. E-mail: sergey.tunik@spbu.ru; Fax: +7 (812) 3241258

Table of Contents Figure S1. 1 H NMR spectrum of [NHC-(CH2)3-NHC(AuX)2] (X=Cl, Br) 5 Figure S2. ESI + mass spectrum of [NHC-CH2-NHC(AuX)2] (X=Cl, Br)..6 Figure S3. ESI + mass spectrum of [NHC-(CH2)2-NHC(AuX)2] (X=Cl, Br)..7 Figure S4. Transformation of complex 7 into 4A and 6PF6 monitored by 1 H NMR.8 Figure S5. 1 H NMR spectra of NHC HBr and NHC HPF6.... 9 Figure S6. 1 H NMR spectrum of complex 5. 10 Figure S7. 1 H NMR spectra of complexes 6PF6 and 6Br....11 Figure S8. 1 H NMR spectrum of complex 4A..12 Figure S9. 1 H NMR spectrum of complex 4B...13 Figure S10. 1 H NMR spectrum of complex 4C...14 Figure S11. 1 H NMR spectra of complexes 1A, 2A, and 3A... 15 Figure S12. 1 H NMR spectra of complexes 1B, 2B, and 3B... 16 Figure S13. 1 H NMR spectra of complexes 1C, 2C, and 3C.... 17 Figure S14. 13 C{ 1 H} NMR spectrum of complex 2A. 18 Figure S15. 13 C{ 1 H} NMR spectrum of complex 3A. 19 Figure S16. 13 C{ 1 H} NMR spectrum of complex 3B..20 Figure S17. 13 C{ 1 H} NMR spectrum of complex 3C..21 Figure S18. ESI + mass spectrum of complex 6Br...22 Figure S19. ESI + mass spectrum of complex 6PF6......23 Figure S20. ESI mass spectrum of 6PF6.24 Figure S21. ESI + mass spectrum of complex 4A..25 Figure S22. ESI + mass spectrum of complex 4B..26 Figure S23. ESI + mass spectrum of complex 4C..27 Figure S24. ESI + mass spectrum of complex 1A..28 2

Figure S25. ESI + mass spectrum of complex 2A.. 29 Figure S26. ESI + mass spectrum of complex 3A.. 30 Figure S27. ESI + mass spectrum of complex 1B. 31 Figure S28. ESI + mass spectrum of complex 2B..32 Figure S29. ESI + mass spectrum of complex 3B.. 33 Figure S30. ESI + mass spectrum of complex 1C..34 Figure S31. ESI + mass spectrum of complex 2C..35 Figure S32. ESI + mass spectrum of complex 3C..36 Figure S33. 1 H NMR spectra of complex 7 and 8.... 37 Figure S34. ESI + mass spectrum of complex 7.38 Figure S35. ESI + mass spectrum of complex 8.39 Figure S36. ESI mass spectrum of complex 7.40 Figure S37. ESI mass spectrum of 8...41 Figure S38. Intermolecular π-stacking in the solid-state structure of complex 7.42 Figure S39. UV/vis spectra of NHC ligand precursors.42 Figure S40. UV/vis spectra of complexes 5, 6PF6, and 6Br 43 Figure S41. UV/vis spectra of alkylalkynyl complexes 1B 4C...44 Figure S42. UV/vis spectra of phenylalkynyl complexes 1A, 2A, 3A, and 4A..45 Figure S43. PXRD pattern of 4A blue..46 Figure S44. Emission spectra of two different batches of crystals of complex 4A..47 Figure S45. PXRD pattern of material in batch 2.48 Figure S46. PXRD pattern of complex 3A...49 Figure S47. Solid-state emission and excitation spectra of 4A blue at rt and 77 K.50 Figure S48. Overlay of the asymmetric units of 4A green at 100 and 260 K..51 Figure S49. Solid-state emission spectra of 1A, 2A, 3A, and 4A green DCM /4A yellow at 77 K.52 Figure S50. Solid-state excitation spectra of 1A, 2A, 3A, and 4A green at 77 K and rt..53 Figure S51. Open and closed structures for complex 3A obtained from DFT calculations 55 Figure S52. Ground-state frontier orbitals of the optimized structure of complex 1A.56 3

Figure S53. Ground-state frontier orbitals of the optimized structure of complex 2A.57 Figure S54. Ground-state frontier orbitals of the optimized structure of complex 3A.58 Table S1. Absorption and emission wavelengths obtained from calculations..59 Figure S55. Spin density map for the lowest triplet state of complex 2A....60 Figure S56. Ground-state frontier orbitals of the dimeric unit of 4A green polymorph..61 Figure S57. Ground-state frontier orbitals of the dimeric unit of 4A yellow polymorph.62 Figure S58. Ground-state frontier orbitals of the trinuclear cationic part of complex 7...63 Table S2. Crystallographic data...65 4

Figure S1. 1 H NMR spectrum of [NHC-(CH2)3-NHC(AuX)2] (X=Cl, Br) (DMSO-d6, rt). 5

Figure S2. ESI + mass spectrum of [NHC-CH2-NHC(AuX)2] (X=Cl, Br). Insets show the experimental isotopic patterns of [C58H48N8BrClAu3] + and [C58H48N8Br2Au3] + (black) along with the calculated ones (red). 6

Figure S3. ESI + mass spectrum of [NHC-(CH2)2-NHC(AuX)2] (X=Cl, Br). Insets show the experimental isotopic patterns of [C30H27N4ClAu] + and [C30H27N4BrAu] + (black) along with the calculated ones (red). 7

Figure S4. Transformation of complex 7 into 4A and 6PF6 monitored by 1 H NMR (DMSO-d6, rt). 8

Figure S5. 1 H NMR spectra of NHC HBr (top) and NHC HPF6 (bottom) (DMSO-d6, rt). 9

Figure S6. 1 H NMR spectrum of complex 5 (DMSO-d6, rt). 10

Figure S7. 1 H NMR spectra of complexes 6PF6 (top) and 6Br (bottom) (DMSO-d6, rt). 11

Figure S8. 1 H NMR spectrum of complex 4A (DMSO-d6, rt). 12

Figure S9. 1 H NMR spectrum of complex 4B (DMSO-d6, rt). 13

Figure S10. 1 H NMR spectrum of complex 4C (DMSO-d6, rt). 14

Figure S11. 1 H NMR spectra of complexes 1A, 2A, and 3A (DMSO-d6, rt). 15

Figure S12. 1 H NMR spectra of complexes 1B, 2B, and 3B (DMSO-d6, rt). 16

Figure S13. 1 H NMR spectra of complexes 1C, 2C, and 3C (DMSO-d6, rt). 17

Figure S14. 13 C{ 1 H} NMR spectrum of complex 2A (CDCl3, rt). 18

Figure S15. 13 C{ 1 H} NMR spectrum of complex 3A (CDCl3, rt). 19

Figure S16. 13 C{ 1 H} NMR spectrum of complex 3B (DMSO-d6, rt). 20

Figure S17. 13 C{ 1 H} NMR spectrum of complex 3C (CDCl3, rt). 21

Figure S18. ESI + mass spectrum of complex 6Br. The inset shows the experimental isotopic pattern of [C30H28N4Au] + (black) along with the calculated one (red). 22

Figure S19. ESI + mass spectrum of complex 6PF6. The inset shows the experimental isotopic pattern of [C30H28N4Au] + (black) along with the calculated one (red). 23

Figure S20. ESI mass spectrum of 6PF6. 24

Figure S21. ESI + mass spectrum of complex 4A. The inset shows the experimental isotopic pattern of [C23H19N2AuNa] + (black) along with the calculated one (red). 25

Figure S22. ESI + mass spectrum of complex 4B. The inset shows the experimental isotopic pattern of [C23H25N2OAuNa] + (black) along with the calculated one (red). 26

Figure S23. ESI + mass spectrum of complex 4C. The inset shows the experimental isotopic pattern of [C20H21N2OAuNa] + (black) along with the calculated one (red). 27

Figure S24. ESI + mass spectrum of complex 1A. The inset shows the experimental isotopic pattern of [C45H34N4Au2Na] + (black) along with the calculated one (red). 28

Figure S25. ESI + mass spectrum of complex 2A. The inset shows the experimental isotopic pattern of [C46H36N4Au2Na] + (black) along with the calculated one (red). 29

Figure S26. ESI + mass spectrum of complex 3A. The inset shows the experimental isotopic pattern of [C47H38N4Au2Na] + (black) along with the calculated one (red). 30

Figure S27. ESI + mass spectrum of complex 1B. The inset shows the experimental isotopic pattern of [C45H46N4O2Au2Na] + (black) along with the calculated one (red). 31

Figure S28. ESI + mass spectrum of complex 2B. The inset shows the experimental isotopic pattern of [C46H48N4O2Au2Na] + (black) along with the calculated one (red). 32

Figure S29. ESI + mass spectrum of complex 3B. The inset shows the experimental isotopic pattern of [C47H50N4O2Au2Na] + (black) along with the calculated one (red). 33

Figure S30. ESI + mass spectrum of complex 1C. The inset shows the experimental isotopic pattern of [C39H38N4O2Au2Na] + (black) along with the calculated one (red). 34

Figure S31. ESI + mass spectrum of complex 2C. The inset shows the experimental isotopic pattern of [C40H40N4O2Au2Na] + (black) along with the calculated one (red). 35

Figure S32. ESI + mass spectrum of complex 3C. The inset shows the experimental isotopic pattern of [C41H42N4O2Au2Na] + (black) along with the calculated one (red). 36

Figure S33. 1 H NMR spectra of complex 7 (green) and 8 (red) (DMSO-d6, rt). The spectrum of 6Br is shown in blue for comparison. Note that for 8, a slight contamination with in situ formed complex 4C is observed. 37

Figure S34. ESI + mass spectrum of complex 7. The inset shows the experimental isotopic pattern of [C30H28N4Au] + (black) along with the calculated one (red). 38

Figure S35. ESI + mass spectrum of complex 8. The inset shows the experimental isotopic pattern of [C30H28N4Au] + (black) along with the calculated one (red). 39

Figure S36. ESI mass spectrum of complex 7. The inset shows the experimental isotopic pattern of [C16H10Au] (black) along with the calculated one (red). 40

Figure S37. ESI mass spectrum of 8. The inset shows the experimental isotopic pattern of [C10H14O2Au] (black) along with the calculated one (red). 41

Figure S38. A fragment of the infinite one-dimensional chain of interpenetrated π-π-linked cations in the solid-state structure of complex 7. Hydrogen atoms and PF6 anions are omitted for clarity. Normalized Absorbance NHC HBr NHC CH 2 NHC 2HBr NHC (CH 2 ) 2 NHC 2HBr NHC (CH 2 ) 3 NHC 2HBr 250 300 350 Wavelength (nm) Figure S39. UV/vis spectra of NHC ligand precursors (NHC HBr in CH2Cl2, the rest in MeOH). 42

Normalized Absorbance 5 6PF 6 6Br 250 300 350 400 Wavelength (nm) Figure S40. UV/vis spectra of complexes 5, 6PF6, and 6Br in CH2Cl2. 43

Normalized Absorbance 4B 4C 1B 2B 3B 1C 2C 3C 250 300 350 400 Wavelength (nm) Figure S41. UV/vis spectra of alkylalkynyl complexes 1B 4C in CH2Cl2. 44

Normalized Absorbance 4A 1A 2A 3A 250 300 350 400 Wavelength (nm) Figure S42. UV/vis spectra of phenylalkynyl complexes 1A, 2A, 3A, and 4A in CH2Cl2. 45

Experimental pattern Calculated pattern of 4A blue 10 20 30 40 50 2Theta (deg) Figure S43. PXRD pattern of 4A blue. 46

Normalized Emission Intensity (a.u.) Batch 1 Batch 2 450 500 550 600 650 700 750 Wavelength (nm) Figure S44. Room-temperature emission spectra of two different batches of crystals of complex 4A. Batch 1 is comprised mostly of 4A green, batch 2 is formulated as a mixture of 4A green DCM and 4A yellow. Excitation wavelength is 350 nm. 47

Sum of the calculated patterns of 4A yellow green DCM and 4A Experimental pattern 10 20 30 40 50 2Theta (deg) Figure S45. PXRD pattern of material in batch 2, formulated as a mixture of 4A green DCM and 4A yellow. 48

Experimental pattern Calculated pattern of 3A 10 20 30 40 50 2Theta (deg) Figure S46. PXRD pattern of complex 3A. 49

Normalized Emission Intensity (a.u.) 350 nm Excitation (rt) 310 nm Excitation (rt) 350 nm Excitation (77 K) 310 nm Excitation (77 K) rt 77 K 300 350 400 450 500 550 600 650 Wavelength (nm) Figure S47. Solid-state emission (solid line) and excitation (dashed line) spectra of 4A blue at room temperature and 77 K. 50

Figure S48. Overlay of the asymmetric units of 4A green at 100 and 260 K. 51

Normalized Emission Intensity (a.u.) 4A green DCM /4A yellow Excitation at 310 nm 4A green DCM /4A yellow Excitation at 350 nm 1A Excitation at 310 nm 1A Excitation at 350 nm 2A Excitation at 310 nm 2A Excitation at 350 nm 3A Excitation at 310 nm 3A Excitation at 350 nm 400 500 600 700 Wavelength (nm) Figure S49. Solid-state emission spectra of 1A, 2A, 3A, and 4A green DCM /4A yellow under 310 and 350 nm excitation at 77 K. 52

Normalized Emission Intensity (a.u.) 4A green 77 K 4A green rt 1A 77 K 1A rt 2A 77 K 2A rt 3A 77 K 3A rt 250 300 350 400 450 Wavelength (nm) Figure S50. Solid-state excitation spectra of 1A, 2A, 3A, and 4A green at 77 K and room temperature. 53

lowest-energy open structure open structure, +4.6 kj/mol open structure, +5.1 kj/mol 54

closed structure, +29.9 kj/mol Figure S51. Open and closed structures for complex 3A obtained from DFT calculations. 55

HOMO 1 HOMO LUMO LUMO+1 Figure S52. Ground-state frontier orbitals of the optimized structure of complex 1A. 56

HOMO 1 HOMO LUMO LUMO+1 Figure S53. Ground-state frontier orbitals of the optimized structure of complex 2A. 57

HOMO 1 HOMO LUMO LUMO+1 Figure S54. Ground-state frontier orbitals of the optimized structure of complex 3A. 58

Table S1. Absorption and emission wavelengths obtained from DFT and TDDFT calculations. Absorption: energy of the lowest singlet state with high oscillator strength observed in TDDFT calculations. Emission: energy gap between the lowest triplet state and the singlet ground state obtained from DFT geometry optimizations. Experimental values are taken from Table 1. Complex Absorption, nm Emission, nm Experiment Calculation Experiment Calculation (solution) 5 281, 289 253 none 348 1A 291 295 424, 444 415 2A 293 294 424, 446 414 3A 292 287 424, 449 413 4A 292 278 421, 446 414 1B 283, 292 283 none 375 2B 281, 290 271 none 333 3B 284, 292 256-259 none 333 4B 283, 292 264 none 312 1C 283, 292 266 none 336 2C 281, 290 266 none 338 3C 283, 292 256-260 none 333 4C 283, 292 250-252 none 311 59

Figure S55. Spin density map for the lowest triplet state of complex 2A. 60

HOMO 1 HOMO LUMO LUMO+1 Figure S56. Ground-state frontier orbitals of the dimeric unit of 4A green polymorph. 61

HOMO 1 HOMO LUMO LUMO+1 Figure S57. Ground-state frontier orbitals of the dimeric unit of 4A yellow polymorph. 62

HOMO 1 HOMO LUMO LUMO+1 Figure S58. Ground-state frontier orbitals of the trinuclear cationic part of complex 7. 63

The solid-state structures of 9 compounds were determined by single crystal X-ray diffraction analyses. For 3A, diffraction data were collected with an Agilent Technologies Excalibur Eos diffractometer at 100 K using monochromated MoKα radiation. Diffraction data for the crystals of all the other compounds were recorded with an Agilent Technologies SuperNova Atlas diffractometer at 100 K (and also at 260 K for 4A green ) using monochromated microfocused CuKα radiation. Empirical absorption correction was applied in the CrysAlisPro 1 program complex using spherical harmonics implemented in SCALE3 ABSPACK scaling algorithm. Using Olex2 2, the structures of 3A, 4A green (both at 100 and 260 K), and 4A green DCM were solved with the ShelXS 3 structure solution program using Direct Methods and refined with the ShelXL 3 refinement package using Least Squares minimisation. All the other structures were solved with the Superflip 4 structure solution program using Charge Flipping and refined with the ShelXL 3 refinement package using Least Squares minimisation. The carbon-bound H atoms were placed in calculated positions and were included in the refinement in the riding model approximation, with Uiso(H) set to 1.5Ueq(C) and C H 0.96 Å for the CH3 groups, Uiso(H) set to 1.2Ueq(C) and C H 0.97 Å for the CH2 groups and Uiso(H) set to 1.2Ueq(C) and C H 0.93 Å for the CH groups. The unit cell parameters and refinement characteristics for the crystal structures of the investigated compounds are given in Table S2. The hygroscopic nature of complex 6Br results in the incorporation of 1.75 water molecules per formula unit. For complex 7, high values of the refinement parameters and rather low bond precision in the structural model are due to the low quality of the crystal and severe disorder. Additionally, the crystal underwent changes in the process of the X-ray experiment. Supplementary crystallographic data for this paper have been deposited at the Cambridge Crystallographic Data Centre and can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif. (1) CrysAlisPro, Agilent Technologies, Version 1.171.36.20 (release 27-06-2012). (2) Dolomanov, O. V; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H. OLEX2: A Complete Structure Solution, Refinement and Analysis Program. J. Appl. Crystallogr. 2009, 42, 339 341. (3) Sheldrick, G. M. A Short History of SHELX. Acta Crystallogr. Sect. A 2008, 64, 112 122. (4) Palatinus, L.; Chapuis, G. SUPERFLIP - a Computer Program for the Solution of Crystal Structures by Charge Flipping in Arbitrary Dimensions. J. Appl. Crystallogr. 2007, 40, 786 790. 64

Table S2. Crystallographic data. Compound 6Br 6PF6 4A blue 4A green (100 K) 4A green (260 K) 4A green DCM 4A yellow Formula C 30H 28N 4AuBr, 1.75H 2O C 30H 28N 4AuPF 6 C 23H 19N 2Au C 23H 19N 2Au C 23H 19N 2Au C 23H 19N 2Au, 0.38CH 2Cl 2 C 23H 19N 2Au Formula weight 752.98 786.51 520.39 520.39 520.39 552.21 520.39 Temperature (K) 100(2) 100(2) 100(2) 100(2) 260(2) 100(2) 100(2) Crystal system monoclinic triclinic monoclinic monoclinic monoclinic triclinic triclinic Space group P2 1/c P-1 P2/c P2 1/c P2 1/c P-1 P-1 a (Å) 10.17440(10) 9.2268(9) 21.804(2) 15.7953(3) 15.9312(4) 11.0210(3) 8.5739(3) b (Å) 39.2954(3) 10.9302(12) 6.1315(6) 11.0898(2) 11.1890(2) 13.7455(5) 9.5725(5) c (Å) 28.6667(3) 14.7579(10) 27.7723(14) 22.3469(4) 22.5890(5) 14.3902(4) 13.0259(7) α ( ) 90.00 85.463(7) 90.00 90.0 90 80.408(3) 97.622(4) β ( ) 103.8070(10) 76.613(7) 90.957(6) 103.8212(19) 103.817(2) 80.949(3) 107.923(4) γ ( ) 90.00 75.738(9) 90.00 90.0 90 69.701(3) 106.084(4) Volume (Å 3 ) 11129.98(18) 1402.9(2) 3712.3(6) 3801.10(12) 3910.05(14) 2004.30(12) 949.22(8) Z 4 2 4 4 4 4 2 ρ calc (mg/mm 3 ) 1.795 1.862 1.862 1.819 1.768 1.830 1.821 μ (mm -1 ) 11.880 11.002 14.940 14.591 14.184 14.776 14.607 F(000) 5864.0 768.0 2000.0 2000.0 2000.0 1063.0 500.0 Crystal size (mm 3 ) 0.30 0.16 0.10 0.3189 0.1327 0.124 0.28 0.22 0.14 0.36 0.10 0.06 0.34 0.10 0.08 0.38 0.08 0.06 0.44 0.12 0.10 2Θ range ( ) 6.74 to 140 6.16 to 140 6.36 to 140 5.762 to 144.992 5.712 to 139.998 9.878 to 139.998 7.34 to 139.98 Index ranges -10 h 12-47 k 47-34 l 34-9 h 11-13 k 12-17 l 14-26 h 26-7 k 6-33 l 33-19 h 15-7 k 13-26 l 27-19 h 16-13 k 8-26 l 26-13 h 12-16 k 16-17 l 17-6 h 10-11 k 11-15 l 15 Reflections collected 103719 9950 37417 16096 15496 28421 8259 Independent reflections 21058 [R(int) = 0.0569] 5313 [R(int) = 0.0667] 7008 [R(int) = 0.0586] 7510 [R(int) = 0.0355] 6222 [R(int) = 0.0645] 7601 [R(int) = 0.0645] 3571 [R(int) = 0.0371] Data/restraints/parameters 21058/0/1270 5313/0/381 7008/0/471 7510/0/471 6222/0/429 7601/0/486 3571/0/236 Goodness-of-fit on F 2 1.100 1.044 1.117 1.022 1.097 1.038 1.098 Final R indexes [I>2σ(I)] R 1 = 0.0601 wr 2 = 0.1518 R 1 = 0.0615 wr 2 = 0.1557 R 1 = 0.0511 wr 2 = 0.1107 R 1 = 0.0313 wr 2 = 0.0756 R 1 = 0.0630 wr 2 = 0.1809 R 1 = 0.0404 wr 2 = 0.1049 R 1 = 0.0343 wr 2 = 0.0942 Final R indexes [all data] R 1 = 0.0642 wr 2 = 0.1549 R 1 = 0.0660 wr 2 = 0.1620 R 1 = 0.0606 wr 2 = 0.1182 R 1 = 0.0396 wr 2 = 0.0810 R 1 = 0.0750 wr 2 = 0.1970 R 1 = 0.0480 wr 2 = 0.1116 R 1 = 0.0352 wr 2 = 0.0951 Largest diff. peak/hole (e Å -3 ) 3.32/-3.03 3.80/-3.94 3.55/-2.20 2.26/-1.27 1.93/-2.15 2.29/-1.79 3.10/-1.27 CCDC 1504381 1504382 1504386 1528375 1528736 1528680 1504387 R 1 = Σ F o F c /Σ F o ; 2 wr 2 = {Σ[w(F o F 2 c ) 2 ]/Σ[w(F 2 o ) 2 ]} 1/2 ; w =1/[σ 2 (F 2 o )+(ap) 2 2 + bp], where P = (F o + 2F 2 2 c )/3; S = {Σ[w(F o F 2 c ) 2 ]/(n p)} 1/2, where n is the number of reflections and p is the number of refinement parameters. 65

Compound 4C 3A 7 Formula C 20H 21N 2OAu C 47H 38N 4Au 2, CH 2Cl 2 C 76H 66N 8Au 3PF 6 Formula weight 502.37 1137.71 1827.28 Temperature (K) 100(2) 100(2) 100(2) Crystal system triclinic triclinic triclinic Space group P-1 P-1 P-1 a (Å) 9.9900(6) 11.0758(4) 10.6954(12) b (Å) 10.4782(5) 13.8593(8) 13.917(2) c (Å) 10.6688(5) 15.1816(9) 13.9599(8) α ( ) 109.565(4) 110.818(5) 108.493(10) β ( ) 106.390(5) 107.771(4) 97.007(8) γ ( ) 109.741(5) 90.271(4) 106.357(13) Volume (Å 3 ) 886.63(8) 2057.47(18) 1839.1(4) Z 2 2 1 ρ calc (mg/mm 3 ) 1.882 1.836 1.650 μ (mm -1 ) 15.646 7.292 11.735 F(000) 484.0 1096.0 884.0 Crystal size (mm 3 ) 0.22 0.16 0.08 0.4915 0.1253 0.0851 0.22 0.14 0.08 2Θ range ( ) 9.82 to 139.94 5.14 to 55 7.12 to 144.98 Index ranges -12 h 11-12 k 12-11 l 12-14 h 14-18 k 18-19 l 19-8 h 13-17 k 17-17 l 14 Reflections collected 11328 24449 13410 Independent reflections 3341 [R(int) = 0.0596] 9431 [R(int) = 0.0428] 7199 [R(int) = 0.0635] Data/restraints/parameters 3341/0/209 9431/0/505 7199/35/194 Goodness-of-fit on F 2 1.101 1.024 1.092 Final R indexes [I>2σ(I)] R 1 = 0.0404 wr 2 = 0.1063 R 1 = 0.0356 wr 2 = 0.0798 R 1 = 0.1303 wr 2 = 0.3058 Final R indexes [all data] R 1 = 0.0424 wr 2 = 0.1078 R 1 = 0.0525 wr 2 = 0.0868 R 1 = 0.1368 wr 2 = 0.3104 Largest diff. peak/hole (e Å -3 ) 2.65/-2.76 2.80/-1.31 5.38/-3.89 CCDC 1504388 1504389 1504380 R 1 = Σ F o F c /Σ F o ; 2 wr 2 = {Σ[w(F o F 2 c ) 2 ]/Σ[w(F 2 o ) 2 ]} 1/2 ; w =1/[σ 2 (F 2 o )+(ap) 2 2 + bp], where P = (F o + 2F 2 2 c )/3; S = {Σ[w(F o F 2 c ) 2 ]/(n p)} 1/2, where n is the number of reflections and p is the number of refinement parameters. 66