<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_1570795
_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         'C30 H35 Ag N2, 0.5(C7 H8)'
_chemical_formula_sum            'C33.5 H39 Ag N2'
_chemical_formula_weight         577.53
_chemical_name_systematic        (IMes)AgMes
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Heat-sensitive,Light-sensitive,Photo-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_block_doi                 10.5517/ccdc.csd.cc2frzz5
_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                109.2690(10)
_cell_angle_beta                 90.0610(10)
_cell_angle_gamma                109.0160(10)
_cell_formula_units_Z            2
_cell_length_a                   10.12120(10)
_cell_length_b                   11.2160(2)
_cell_length_c                   14.9017(2)
_cell_measurement_reflns_used    36787
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      80.0520
_cell_measurement_theta_min      3.0810
_cell_volume                     1498.50(4)
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.911
_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     32.00  58.00   0.50    0.06    --   49.52  77.00   0.00   52
  2  \w     30.00  56.00   0.50    0.06    --   49.52  77.00 -30.00   52
  3  \w     97.00 122.00   0.50    0.06    --   49.52  77.00   0.00   50
  4  \w     95.00 121.00   0.50    0.06    --   58.00  76.00  85.03   52
  5  \w     34.00  60.00   0.50    0.06    --   54.00  77.00 133.60   52
  6  \w     38.00  64.00   0.50    0.06    --   58.00  75.00  73.57   52
  7  \w     39.00  74.00   0.50    0.06    --   58.00  76.00  85.03   70
  8  \w     48.00  74.00   0.50    0.06    --   66.00  74.00  48.95   52
  9  \w     42.00  76.00   0.50    0.06    --   62.00  75.00-126.36   68
 10  \w     44.00  70.00   0.50    0.06    --   62.00  70.00-146.90   52
 11  \w     34.00  64.00   0.50    0.06    --   54.00  75.00-178.94   60
 12  \w     83.00 109.00   0.50    0.06    --   54.00  75.00-178.94   52
 13  \w     42.00  67.00   0.50    0.06    --   54.00  69.00  32.81   50
 14  \w     93.00 123.00   0.50    0.26    --  111.50 150.00  19.00   60
 15  \w     96.00 166.00   0.50    0.26    --  111.50 125.00 -30.00  140
 16  \w    118.00 143.00   0.50    0.26    --  111.50 123.00-142.00   50
 17  \w    -84.00 -20.00   0.50    0.26    --  -90.00  77.00  90.00  128
 18  \w    -63.00 -21.00   0.50    0.26    --  -90.00  57.00  30.00   84
 19  \w    -63.00 -30.00   0.50    0.26    --  -90.00  57.00 -30.00   66
 20  \w    -62.00 -19.00   0.50    0.26    --  -90.00  57.00-120.00   86
 21  \w    -65.00 -19.00   0.50    0.26    --  -90.00  57.00-180.00   92
 22  \w    -78.00 -53.00   0.50    0.06    --  -49.52 -19.00 -60.00   50
 23  \w   -121.00 -92.00   0.50    0.06    --  -49.52 -19.00 -60.00   58
 24  \w    -97.00 -71.00   0.50    0.06    --  -49.52 -77.00-120.00   52
 25  \w    -54.00 -29.00   0.50    0.06    --  -49.52 -77.00-120.00   50
 26  \w    -57.00 -29.00   0.50    0.06    --  -49.52 -77.00  60.00   56
 27  \w   -106.00 -80.00   0.50    0.06    --  -49.52 -77.00  60.00   52
 28  \w    -84.00 -38.00   0.50    0.06    --  -49.52 123.00-142.00   92
 29  \w    -75.00 -50.00   0.50    0.26    --  -90.00 123.00-142.00   50
 30  \w    -57.00 -31.00   0.50    0.26    --  -90.00 150.00  19.00   52
 31  \w    -89.00 -64.00   0.50    0.26    --  -90.00 150.00  19.00   50
 32  \w    -89.00 -64.00   0.50    0.06    --  -49.52 150.00  19.00   50
 33  \w    -19.00   7.00   0.50    0.06    --   14.00 103.00  14.20   52
 34  \w    -18.00  17.00   0.50    0.06    --   14.00 101.00  35.66   70
 35  \w     -1.00  24.00   0.50    0.06    --   30.00  98.00 139.89   50
 36  \w     13.00  38.00   0.50    0.06    --   34.00  83.00 -59.83   50
 37  \w    -15.00  12.00   0.50    0.06    --   14.00 100.00-120.37   54
 38  \w     42.00  84.00   0.50    0.26    --  111.50 -77.00 120.00   84
 39  \w     75.00 101.00   0.50    0.26    --  111.50-123.00 137.00   52
 40  \w     63.00  88.00   0.50    0.06    --   49.52-123.00 137.00   50
 41  \w     43.00 105.00   0.50    0.26    --  111.50-125.00   0.00  124
 42  \w     94.00 121.00   0.50    0.26    --  111.50-150.00 -24.00   54
 43  \w     42.00 105.00   0.50    0.26    --  111.50 -99.00  60.00  126
 44  \w     41.00 105.00   0.50    0.26    --  111.50 -99.00   0.00  128
 45  \w     60.00  87.00   0.50    0.26    --  111.50 -99.00 -90.00   54
 46  \w     81.00 106.00   0.50    0.26    --  111.50 -99.00-180.00   50
 47  \w     48.00  76.00   0.50    0.26    --  111.50 -99.00-180.00   56
 48  \w     51.00  86.00   0.50    0.06    --   49.52-150.00 -24.00   70
 49  \w   -105.00 -69.00   0.50    0.26    --  -90.00 -77.00 150.00   72
 50  \w   -159.00-112.00   0.50    0.26    --  -90.00 -77.00 150.00   94
 51  \w   -124.00 -69.00   0.50    0.26    --  -90.00 -77.00 120.00  110
 52  \w    -98.00 -72.00   0.50    0.26    --  -90.00 -77.00  90.00   52
 53  \w   -156.00-114.00   0.50    0.26    --  -90.00 -77.00  90.00   84
 54  \w   -160.00-131.00   0.50    0.26    --  -90.00 -77.00   0.00   58
 55  \w   -149.00-117.00   0.50    0.26    --  -90.00 -77.00 -30.00   64
 56  \w   -110.00 -71.00   0.50    0.26    --  -90.00 -77.00   0.00   78
 57  \w    -96.00 -71.00   0.50    0.26    --  -90.00 -77.00 -30.00   50
 58  \w    -96.00 -71.00   0.50    0.26    --  -90.00 -77.00  30.00   50
 59  \w    -97.00 -72.00   0.50    0.26    --  -90.00 -77.00 -90.00   50
 60  \w   -143.00-114.00   0.50    0.26    --  -90.00 -77.00 -90.00   58
 61  \w   -144.00-118.00   0.50    0.26    --  -90.00 -77.00-180.00   52
 62  \w   -105.00 -70.00   0.50    0.26    --  -90.00 -77.00-180.00   70
 63  \w   -159.00-118.00   0.50    0.26    --  -90.00 -74.00-131.50   82
 64  \w    -97.00 -70.00   0.50    0.26    --  -90.00 -74.00-162.69   54
 65  \w    -85.00 -59.00   0.50    0.26    --  -78.00 -74.00   1.27   52
 66  \w   -109.00 -69.00   0.50    0.26    --  -90.00 -77.00  60.00   80
 67  \w   -105.00 -73.00   0.50    0.26    --  -90.00 -74.00 135.51   64
 68  \w   -150.00-125.00   0.50    0.26    --  -90.00 -77.00  60.00   50
 69  \w   -140.00-115.00   0.50    0.26    --  -82.00 -73.00  13.40   50
 70  \w    -88.00 -63.00   0.50    0.26    --  -82.00 -73.00  13.40   50
 71  \w   -155.00-129.00   0.50    0.26    --  -90.00 -74.00 -86.34   52
 72  \w   -132.00 -73.00   0.50    0.26    --  -90.00 -73.00 -59.87  118
 73  \w    -97.00 -72.00   0.50    0.26    --  -90.00 -74.00-131.50   50
 74  \w    -97.00 -72.00   0.50    0.26    --  -90.00 -74.00 -86.34   50
 75  \w    -97.00 -72.00   0.50    0.26    --  -90.00 -71.00 -28.31   50
 76  \w    -86.00 -60.00   0.50    0.26    --  -78.00 -72.00  14.80   52
 77  \w    -81.00 -55.00   0.50    0.26    --  -74.00 -72.00  97.30   52
 78  \w    -80.00 -55.00   0.50    0.26    --  -74.00 -72.00 179.54   50
 79  \w    -99.00 -74.00   0.50    0.26    --  -90.00 -66.00-128.88   50
 80  \w    -82.00 -55.00   0.50    0.26    --  -70.00 -65.00-126.15   54
 81  \w    -98.00 -73.00   0.50    0.26    --  -90.00 -70.00-178.29   50
 82  \w   -133.00-106.00   0.50    0.26    --  -90.00 -70.00-178.29   54
 83  \w   -158.00-125.00   0.50    0.26    --  -90.00 -66.00-128.88   66
 84  \w   -157.00 -75.00   0.50    0.26    --  -90.00 -65.00-113.98  164
 85  \w    -83.00 -58.00   0.50    0.26    --  -74.00 -64.00-105.91   50
 86  \w    -83.00 -58.00   0.50    0.26    --  -74.00 -64.00 -82.17   50
 87  \w   -124.00 -74.00   0.50    0.26    --  -90.00 -64.00 -29.00  100
 88  \w   -155.00-127.00   0.50    0.26    --  -90.00 -64.00 -29.00   56
 89  \w   -154.00-128.00   0.50    0.26    --  -90.00 -65.00  25.10   52
 90  \w    -84.00 -50.00   0.50    0.06    --  -66.00 -65.00 137.76   68
 91  \w   -121.00 -74.00   0.50    0.26    --  -90.00 -65.00  25.10   94
 92  \w    -88.00 -56.00   0.50    0.26    --  -70.00 -61.00  32.28   64
 93  \w    -82.00 -56.00   0.50    0.26    --  -70.00 -61.00 -49.88   52
 94  \w    -92.00 -66.00   0.50    0.26    --  -82.00 -64.00 -67.14   52
 95  \w    -76.00 -50.00   0.50    0.06    --  -66.00 -64.00-120.14   52
 96  \w    -76.00 -51.00   0.50    0.06    --  -66.00 -63.00 -70.47   50
 97  \w   -151.00 -77.00   0.50    0.26    --  -90.00 -59.00  -9.55  148
 98  \w   -146.00-121.00   0.50    0.26    --  -90.00 -55.00  70.31   50
 99  \w    -92.00 -67.00   0.50    0.26    --  -78.00 -57.00 125.56   50
100  \w   -114.00 -78.00   0.50    0.26    --  -90.00 -55.00  70.31   72
101  \w   -160.00-104.00   0.50    0.26    --  -90.00 -38.00 150.00  112
102  \w   -110.00 -84.00   0.50    0.26    --  -90.00 -54.00-166.46   52
103  \w   -160.00-135.00   0.50    0.26    --  -90.00 -54.00-166.46   50
104  \w   -117.00 -79.00   0.50    0.06    --  -49.52-150.00 -24.00   76
105  \w   -127.00-102.00   0.50    0.26    --  -90.00-150.00 -24.00   50
106  \w   -161.00 -86.00   0.50    0.26    --  -90.00-123.00 137.00  150
107  \w   -121.00 -96.00   0.50    0.06    --  -49.52-123.00 137.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0385
_diffrn_reflns_av_unetI/netI     0.0184
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.911
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            40595
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.911
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.627
_diffrn_reflns_theta_min         3.165
_exptl_absorpt_coefficient_mu    5.550
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63853
_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    1.280
_exptl_crystal_description       block
_exptl_crystal_F_000             602
_exptl_crystal_preparation       'Prepared from IMesAgCl and Mes2Mg'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Toluene'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.610
_refine_diff_density_min         -0.626
_refine_diff_density_rms         0.068
_refine_ls_extinction_coef       0.00199(16)
_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   1.098
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     388
_refine_ls_number_reflns         5930
_refine_ls_number_restraints     136
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0260
_refine_ls_R_factor_gt           0.0259
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0420P)^2^+1.0741P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0715
_refine_ls_wR_factor_ref         0.0716
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5880
_reflns_number_total             5930
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04067d2.cif
_cod_data_source_block           ch-104-nhc_ag-mes_auto
_cod_depositor_comments
'Adding full bibliography for 1570794--1570800.cif.'
_cod_original_formula_sum        'C33.50 H39 Ag N2'
_cod_database_code               1570795
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.490
_shelx_estimated_absorpt_t_min   0.287
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C37-C31
 1.51 with sigma of 0.02
 C31-C32 = C31-C36 = C33-C34
 1.39 with sigma of 0.02
 C32-C33 = C34-C35 = C35-C36
 1.38 with sigma of 0.02
 C31-C35
 2.41 with sigma of 0.04
 C33-C35 = C34-C36
 2.4 with sigma of 0.04
 C31-C33
 2.42 with sigma of 0.04
 C32-C34
 2.39 with sigma of 0.04
 C37-C32 = C37-C36
 2.52 with sigma of 0.04
 C31-C32 \\sim C32-C33 \\sim C33-C34 \\sim C34-C35 \\sim C35-C36 \\sim C36-C31
 with sigma of 0.02
 C31-C35 \\sim C31-C33 \\sim C36-C34 \\sim C32-C36 \\sim C33-C35 \\sim C32-C34
 with sigma of 0.04
 C37-C36 \\sim C37-C32
 with sigma of 0.04
3. Restrained planarity
 C37, C31, C32, C33, C34, C35, C36
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C37 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C37, C31, C32, C33, C34, C35, C36
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: C37(0.5) H37a(0.5) H37b(0.5) H37c(0.5) C31(0.5) C32(0.5) H32(0.5)
 C33(0.5) H33(0.5) C34(0.5) H34(0.5) C35(0.5) H35(0.5) C36(0.5) H36(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C26(H26), C24(H24), C32(H32), C33(H33), C34(H34), C35(H35),
 C36(H36)
7.b Idealised Me refined as rotating group:
 C10(H10a,H10b,H10c), C11(H11a,H11b,H11c), C19(H19a,H19b,H19c), C20(H20a,H20b,
 H20c), C12(H12a,H12b,H12c), C29(H29a,H29b,H29c), C30(H30a,H30b,H30c), C21(H21a,
 H21b,H21c), C28(H28a,H28b,H28c), C37(H37a,H37b,H37c)
;
_shelx_res_checksum              62066
_olex2_exptl_crystal_mounting_method 'XRD Oil and Kapton'
_olex2_submission_original_sample_id CH104
_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
;