<sup>109</sup>Ag NMR chemical shift as a descriptor for Brønsted acidity from molecules to materials.
Hansen, Colin; Docherty, Scott R.; Cao, Weicheng; Yakimov, Alexander V.; Copéret, Christophe; Chemical science 15 (2024) 3028–3032; doi:10.1039/d3sc04067d

data_1570794
_publ_section_title
;
 <sup>109</sup>Ag NMR chemical shift as a descriptor for Br&#xf8;nsted
 acidity from molecules to materials.
;
_journal_issue                   8
_journal_name_full               'Chemical science'
_journal_page_first              3028
_journal_page_last               3032
_journal_paper_doi               10.1039/d3sc04067d
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C36 H49 Ag N2 O'
_chemical_formula_sum            'C36 H49 Ag N2 O'
_chemical_formula_weight         633.64
_chemical_name_common            (SIMes)AgBHT
_chemical_name_systematic        (SIMes)AgOAr
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Heat-sensitive,Light-sensitive,Photo-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2frzx3
_audit_creation_date             2023-04-19
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-04-19 deposited with the CCDC.	2024-01-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.6160(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.6810(2)
_cell_length_b                   13.7656(2)
_cell_length_c                   22.8895(4)
_cell_measurement_reflns_used    74595
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      80.1450
_cell_measurement_theta_min      3.2830
_cell_volume                     3358.75(10)
_computing_cell_refinement       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -49.00  22.00   0.50    0.19    --  -49.52  92.00 165.00  142
  2  \w    -17.00  71.00   0.50    0.19    --   49.52 -92.00  52.00  176
  3  \w   -145.00-120.00   0.50    0.74    --  -90.00 -92.00  52.00   50
  4  \w    -54.00 -29.00   0.50    0.74    --  -90.00  92.00 165.00   50
  5  \w     67.00  93.00   0.50    0.74    --  111.50 -92.00  52.00   52
  6  \w    120.00 157.00   0.50    0.74    --  111.50  92.00 165.00   74
  7  \w   -110.00 -60.00   0.50    0.19    --  -49.52 -77.00  60.00  100
  8  \w   -116.00 -39.00   0.50    0.19    --  -49.52 -77.00 120.00  154
  9  \w     29.00  80.00   0.50    0.19    --   49.52  77.00  90.00  102
 10  \w     90.00 118.00   0.50    0.19    --   49.52  57.00  60.00   56
 11  \w     39.00  75.00   0.50    0.19    --   49.52  57.00  60.00   72
 12  \w     42.00  78.00   0.50    0.19    --   49.52  38.00  60.00   72
 13  \w     66.00  92.00   0.50    0.19    --   49.52-125.00-120.00   52
 14  \w   -129.00-103.00   0.50    0.74    --  -90.00 -75.00 129.31   52
 15  \w   -102.00 -76.00   0.50    0.74    --  -90.00 -59.00 115.51   52
 16  \w    -99.00 -73.00   0.50    0.74    --  -90.00 -69.00  64.46   52
 17  \w   -160.00-103.00   0.50    0.74    --  -90.00 -77.00 150.00  114
 18  \w    -94.00 -69.00   0.50    0.74    --  -90.00 -77.00 150.00   50
 19  \w    -95.00 -70.00   0.50    0.74    --  -90.00 -75.00 129.31   50
 20  \w    -97.00 -72.00   0.50    0.74    --  -90.00 -72.00  35.59   50
 21  \w    -96.00 -70.00   0.50    0.74    --  -90.00 -75.00  98.28   52
 22  \w    -94.00 -69.00   0.50    0.74    --  -90.00 -77.00  60.00   50
 23  \w    -98.00 -72.00   0.50    0.74    --  -90.00 -72.00 102.69   52
 24  \w    -98.00 -71.00   0.50    0.74    --  -90.00 -73.00  61.61   54
 25  \w    -94.00 -69.00   0.50    0.74    --  -90.00 -77.00  72.55   50
 26  \w    -99.00 -74.00   0.50    0.74    --  -90.00 -65.00  38.19   50
 27  \w   -100.00 -73.00   0.50    0.74    --  -90.00 -76.00 128.55   54
 28  \w    -95.00 -70.00   0.50    0.74    --  -90.00 -76.00  83.11   50
 29  \w    -96.00 -71.00   0.50    0.74    --  -90.00 -72.00  45.01   50
 30  \w    -99.00 -73.00   0.50    0.74    --  -90.00 -77.00  30.00   52
 31  \w    -96.00 -70.00   0.50    0.74    --  -90.00 -76.00  93.33   52
 32  \w    -97.00 -72.00   0.50    0.74    --  -90.00 -70.00 113.41   50
 33  \w    -94.00 -69.00   0.50    0.74    --  -90.00 -77.00 120.00   50
 34  \w    -94.00 -69.00   0.50    0.74    --  -90.00 -77.00  90.00   50
 35  \w    -96.00 -71.00   0.50    0.74    --  -90.00 -73.00  89.99   50
 36  \w     92.00 125.00   0.50    0.74    --  111.50  77.00  60.00   66
 37  \w    103.00 176.00   0.50    0.74    --  111.50  45.00-180.00  146
 38  \w     98.00 133.00   0.50    0.74    --  111.50  61.00 150.00   70
 39  \w     62.00  99.00   0.50    0.74    --  111.50 -77.00 -60.00   74
 40  \w     98.00 123.00   0.50    0.74    --  111.50  61.00 -90.00   50
 41  \w    153.00 178.00   0.50    0.74    --  111.50  61.00  60.00   50
 42  \w     42.00 104.00   0.50    0.74    --  111.50 -77.00-150.00  124
 43  \w    108.00 133.00   0.50    0.74    --  111.50  30.00 150.00   50
 44  \w    128.00 162.00   0.50    0.74    --  111.50 125.00-150.00   68
 45  \w     97.00 138.00   0.50    0.74    --  111.50  61.00  60.00   82
 46  \w    153.00 178.00   0.50    0.74    --  111.50  77.00 120.00   50
 47  \w     91.00 127.00   0.50    0.74    --  111.50  77.00 120.00   72
 48  \w    142.00 168.00   0.50    0.74    --  111.50  61.00  90.00   52
 49  \w     41.00  66.00   0.50    0.74    --  111.50 -61.00 -30.00   50
 50  \w     41.00  70.00   0.50    0.74    --  111.50 -61.00 -60.00   58
 51  \w    153.00 178.00   0.50    0.74    --  111.50  45.00  30.00   50
 52  \w    108.00 143.00   0.50    0.74    --  111.50  45.00  30.00   70
 53  \w    107.00 168.00   0.50    0.74    --  111.50  61.00   0.00  122
 54  \w     49.00  75.00   0.50    0.74    --  111.50 -95.00 -90.00   52
 55  \w     78.00 105.00   0.50    0.74    --  111.50 -77.00  30.00   54
 56  \w    140.00 167.00   0.50    0.74    --  111.50  61.00 -30.00   54
 57  \w    116.00 142.00   0.50    0.74    --  111.50 125.00  60.00   52
 58  \w     41.00 104.00   0.50    0.74    --  111.50 -77.00 -30.00  126
 59  \w     95.00 120.00   0.50    0.74    --  111.50  70.00-149.64   50
 60  \w    147.00 177.00   0.50    0.74    --  111.50  30.00 150.00   60
 61  \w     54.00  96.00   0.50    0.74    --  111.50-125.00 -90.00   84
 62  \w    141.00 177.00   0.50    0.74    --  111.50  61.00 -90.00   72
 63  \w    137.00 162.00   0.50    0.74    --  111.50 105.00-160.44   50
 64  \w     42.00  69.00   0.50    0.74    --  111.50 -95.00-150.00   54
 65  \w     73.00 104.00   0.50    0.74    --  111.50 -95.00-150.00   62
 66  \w     66.00  99.00   0.50    0.74    --  111.50 -95.00 150.00   66
 67  \w     64.00  90.00   0.50    0.74    --  111.50 -77.00  90.00   52
 68  \w     95.00 120.00   0.50    0.74    --  111.50 125.00  30.00   50
 69  \w    104.00 133.00   0.50    0.74    --  111.50  30.00   0.00   58
 70  \w    146.00 173.00   0.50    0.74    --  111.50  61.00 -60.00   54
 71  \w     97.00 125.00   0.50    0.74    --  111.50  61.00  90.00   56
 72  \w    103.00 129.00   0.50    0.74    --  111.50  45.00 -30.00   52
 73  \w     47.00  96.00   0.50    0.74    --  111.50 -77.00-120.00   98
 74  \w     75.00 107.00   0.50    0.74    --  111.50-125.00  60.00   64
 75  \w     63.00 100.00   0.50    0.74    --  111.50 -77.00  60.00   74
 76  \w    127.00 158.00   0.50    0.74    --  111.50 125.00-120.00   62
 77  \w     86.00 111.00   0.50    0.74    --  111.50-125.00  90.00   50
 78  \w     43.00  68.00   0.50    0.74    --  111.50-125.00  60.00   50
 79  \w     41.00  68.00   0.50    0.74    --  111.50 -61.00  60.00   54
 80  \w    131.00 156.00   0.50    0.74    --  111.50  15.00 120.00   50
 81  \w    115.00 140.00   0.50    0.74    --  111.50  30.00  60.00   50
 82  \w     41.00  75.00   0.50    0.74    --  111.50-125.00  90.00   68
 83  \w     86.00 111.00   0.50    0.74    --  111.50-125.00-150.00   50
 84  \w     42.00  71.00   0.50    0.74    --  111.50-125.00-150.00   58
 85  \w     92.00 119.00   0.50    0.74    --  111.50  77.00  90.00   54
 86  \w     48.00 102.00   0.50    0.74    --  111.50 -77.00 150.00  108
 87  \w    142.00 175.00   0.50    0.74    --  111.50  77.00  30.00   66
 88  \w     99.00 147.00   0.50    0.74    --  111.50  61.00  30.00   96
 89  \w     73.00 104.00   0.50    0.74    --  111.50 -95.00 -60.00   62
 90  \w     42.00 110.00   0.50    0.74    --  111.50-125.00 -30.00  136
 91  \w    109.00 134.00   0.50    0.74    --  111.50  30.00-120.00   50
 92  \w    150.00 175.00   0.50    0.74    --  111.50  30.00-120.00   50
 93  \w    107.00 138.00   0.50    0.74    --  111.50  78.00 110.21   62
 94  \w    134.00 159.00   0.50    0.74    --  111.50  30.00   0.00   50
 95  \w    134.00 160.00   0.50    0.74    --  111.50  30.00  30.00   52
 96  \w    123.00 149.00   0.50    0.74    --  111.50  45.00 -60.00   52
 97  \w    123.00 167.00   0.50    0.74    --  111.50  45.00  60.00   88
 98  \w     91.00 117.00   0.50    0.74    --  111.50  77.00 150.00   52
 99  \w    111.00 164.00   0.50    0.74    --  111.50  30.00 120.00  106
100  \w     52.00  77.00   0.50    0.74    --  111.50 -85.00-177.08   50
101  \w     87.00 112.00   0.50    0.74    --  111.50 -85.00-177.08   50
102  \w    110.00 157.00   0.50    0.74    --  111.50   0.00  90.00   94
103  \w     94.00 123.00   0.50    0.74    --  111.50  77.00  30.00   58
104  \w     57.00  83.00   0.50    0.74    --  111.50 -95.00  90.00   52
105  \w     99.00 124.00   0.50    0.74    --  111.50  61.00-120.00   50
106  \w     99.00 134.00   0.50    0.74    --  111.50  61.00 -30.00   70
107  \w    153.00 178.00   0.50    0.74    --  111.50  30.00-150.00   50
108  \w    130.00 155.00   0.50    0.74    --  111.50 125.00 -60.00   50
109  \w    121.00 147.00   0.50    0.74    --  111.50  30.00-150.00   52
110  \w    151.00 178.00   0.50    0.74    --  111.50 125.00  60.00   54
111  \w    106.00 131.00   0.50    0.74    --  111.50 125.00  90.00   50
112  \w    141.00 166.00   0.50    0.74    --  111.50 125.00 150.00   50
113  \w     86.00 111.00   0.50    0.74    --  111.50-125.00  30.00   50
114  \w     99.00 124.00   0.50    0.74    --  111.50  77.00 -60.00   50
115  \w     46.00  77.00   0.50    0.74    --  111.50-125.00 -60.00   62
116  \w    121.00 147.00   0.50    0.74    --  111.50 132.00  50.11   52
117  \w     41.00  67.00   0.50    0.74    --  111.50 -95.00 120.00   52
118  \w    133.00 173.00   0.50    0.74    --  111.50 125.00  30.00   80
119  \w    137.00 174.00   0.50    0.74    --  111.50  77.00  60.00   74
120  \w     46.00  71.00   0.50    0.74    --  111.50 -61.00  30.00   50
121  \w     98.00 125.00   0.50    0.74    --  111.50  61.00 120.00   54
122  \w     41.00  66.00   0.50    0.74    --  111.50 -61.00-150.00   50
123  \w     43.00  69.00   0.50    0.74    --  111.50 -61.00 -90.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1347089000
_diffrn_orient_matrix_UB_12      -0.0014919000
_diffrn_orient_matrix_UB_13      0.0204782000
_diffrn_orient_matrix_UB_21      -0.0469396000
_diffrn_orient_matrix_UB_22      -0.0467011000
_diffrn_orient_matrix_UB_23      -0.0584822000
_diffrn_orient_matrix_UB_31      0.0235538000
_diffrn_orient_matrix_UB_32      -0.1016614000
_diffrn_orient_matrix_UB_33      0.0265823000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0344
_diffrn_reflns_av_unetI/netI     0.0144
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            97033
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.554
_diffrn_reflns_theta_min         3.749
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.016
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76169
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.121a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.253
_exptl_crystal_description       block
_exptl_crystal_F_000             1336
_exptl_crystal_preparation       'Prepared from SIMesAgMes and HOAr'
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: Et2O'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.497
_refine_diff_density_min         -0.510
_refine_diff_density_rms         0.070
_refine_ls_extinction_coef       0.00039(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.146
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     375
_refine_ls_number_reflns         7368
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.146
_refine_ls_R_factor_all          0.0266
_refine_ls_R_factor_gt           0.0262
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0381P)^2^+2.2609P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0737
_refine_ls_wR_factor_ref         0.0740
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7222
_reflns_number_total             7368
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04067d2.cif
_cod_data_source_block           exp_1299_auto
_cod_depositor_comments
'Adding full bibliography for 1570794--1570800.cif.'
_cod_database_code               1570794
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ag C H N O'
_chemical_oxdiff_usercomment     'red bloc'
_shelx_estimated_absorpt_t_max   0.634
_shelx_estimated_absorpt_t_min   0.434
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B)
2.b Aromatic/amide H refined with riding coordinates:
 C32(H32), C8(H8), C21(H21), C6(H6), C23(H23), C30(H30)
2.c Idealised Me refined as rotating group:
 C34(H34A,H34B,H34C), C11(H11A,H11B,H11C), C26(H26A,H26B,H26C), C12(H12A,H12B,
 H12C), C14(H14A,H14B,H14C), C13(H13A,H13B,H13C), C25(H25A,H25B,H25C), C16(H16A,
 H16B,H16C), C35(H35A,H35B,H35C), C17(H17A,H17B,H17C), C36(H36A,H36B,H36C),
 C18(H18A,H18B,H18C), C27(H27A,H27B,H27C)
;
_shelx_res_checksum              33405
_olex2_exptl_crystal_mounting_method 'XRD oil and Kapton'
_olex2_submission_original_sample_id CH129
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.464
_oxdiff_exptl_absorpt_empirical_full_min 0.689