Heavier alkaline earth and heterobimetallic s-block "ate" complexes of a di(amido)siloxane ligand: solid-state structure and dynamic solution-phase behaviour.
Haynes, Matthew D.; O'Reilly, Andrea; Poole, Alice J. M.; Roper, Aisling F.; Thum, Stefan; Morris, Louis J.; Coles, Martyn P.; Fulton, J. Robin; Harder, Sjoerd; Turner, Zoë R; O'Hare, Dermot; Dalton transactions (Cambridge, England : 2003) 54 (2025) 4542–4555; doi:10.1039/d5dt00044k

data_7718004
_publ_section_title
;
 Heavier alkaline earth and heterobimetallic s-block "ate" complexes of a
 di(amido)siloxane ligand: solid-state structure and dynamic
 solution-phase behaviour.
;
_journal_issue                   11
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              4542
_journal_page_last               4555
_journal_paper_doi               10.1039/d5dt00044k
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C56 H92 Ca2 N4 O2 Si4, C6 H6'
_chemical_formula_sum            'C62 H98 Ca2 N4 O2 Si4'
_chemical_formula_weight         1123.96
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2023-12-05
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-12-18 deposited with the CCDC.	2025-02-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.0940(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   30.8158(2)
_cell_length_b                   10.58490(10)
_cell_length_c                   19.6876(2)
_cell_measurement_reflns_used    54135
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      76.4490
_cell_measurement_theta_min      3.7090
_cell_volume                     6405.36(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5035
_diffrn_detector_type            Atlas
_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     -5.00  33.00   1.00    1.00    --  -41.65  19.00 -90.00   38
  2  \w    -10.00  26.00   1.00    1.00    --  -41.65  37.00 120.00   36
  3  \w    -21.00  30.00   1.00    1.00    --  -41.65  37.00-150.00   51
  4  \w    -19.00  30.00   1.00    1.00    --  -41.65  37.00 150.00   49
  5  \w   -111.00 -19.00   1.00    1.00    --  -41.65 -37.00  30.00   92
  6  \w     92.00 163.00   1.00    4.00    --  111.00  61.00 150.00   71
  7  \w     42.00  69.00   1.00    4.00    --  111.00 -61.00-120.00   27
  8  \w     46.00  72.00   1.00    4.00    --  111.00 -45.00   0.00   26
  9  \w     41.00 120.00   1.00    4.00    --  111.00 -77.00-150.00   79
 10  \w    114.00 141.00   1.00    4.00    --  111.00 111.00-180.00   27
 11  \w     42.00  71.00   1.00    4.00    --  111.00 -45.00  30.00   29
 12  \w     45.00  71.00   1.00    4.00    --  111.00 -45.00 -90.00   26
 13  \w     40.00  66.00   1.00    4.00    --  111.00 -45.00 -30.00   26
 14  \w     40.00  70.00   1.00    4.00    --  111.00 -45.00  60.00   30
 15  \w     54.00 123.00   1.00    4.00    --  111.00 -77.00   0.00   69
 16  \w     58.00  92.00   1.00    4.00    --  111.00 -61.00  60.00   34
 17  \w     61.00  87.00   1.00    4.00    --  111.00 -61.00  90.00   26
 18  \w     45.00 106.00   1.00    4.00    --  111.00-111.00 -30.00   61
 19  \w     96.00 140.00   1.00    4.00    --  111.00 153.00-169.00   44
 20  \w     46.00  71.00   1.00    4.00    --  111.00 -45.00 150.00   25
 21  \w    104.00 133.00   1.00    4.00    --  111.00  61.00 120.00   29
 22  \w    152.00 177.00   1.00    4.00    --  111.00  61.00 120.00   25
 23  \w     47.00  72.00   1.00    4.00    --  111.00 -45.00 -60.00   25
 24  \w    112.00 155.00   1.00    4.00    --  111.00  30.00 120.00   43
 25  \w    -86.00 -43.00   1.00    1.00    --  -41.65 125.00-150.00   43
 26  \w     -5.00  28.00   1.00    1.00    --  -41.65  19.00   0.00   33
 27  \w    -21.00   4.00   1.00    1.00    --  -41.65  37.00  30.00   25
 28  \w    -39.00 -12.00   1.00    1.00    --  -41.65 125.00-150.00   27
 29  \w     40.00  86.00   1.00    1.00    --   41.65-125.00   0.00   46
 30  \w     51.00  87.00   1.00    1.00    --   41.65-125.00 150.00   36
 31  \w     20.00  46.00   1.00    1.00    --   41.65 -99.00 -60.00   26
 32  \w     68.00 109.00   1.00    4.00    --  111.00-111.00-120.00   41
 33  \w     55.00 108.00   1.00    4.00    --  111.00-111.00   0.00   53
 34  \w     40.00  65.00   1.00    4.00    --  111.00 -45.00-120.00   25
 35  \w     83.00 109.00   1.00    4.00    --  111.00-111.00 -30.00   26
 36  \w    113.00 142.00   1.00    4.00    --  111.00  45.00-150.00   29
 37  \w     82.00 108.00   1.00    4.00    --  111.00-111.00  60.00   26
 38  \w     70.00 105.00   1.00    4.00    --  111.00-111.00  90.00   35
 39  \w     40.00  77.00   1.00    4.00    --  111.00-111.00  60.00   37
 40  \w     93.00 133.00   1.00    4.00    --  111.00  45.00 -60.00   40
 41  \w    107.00 141.00   1.00    4.00    --  111.00 111.00  90.00   34
 42  \w     84.00 109.00   1.00    4.00    --  111.00-111.00 -90.00   25
 43  \w     56.00  82.00   1.00    4.00    --  111.00-111.00 -90.00   26
 44  \w     65.00  91.00   1.00    4.00    --  111.00-111.00-180.00   26
 45  \w     70.00  96.00   1.00    4.00    --  111.00-111.00  30.00   26
 46  \w     83.00 109.00   1.00    4.00    --  111.00-111.00 150.00   26
 47  \w     46.00 107.00   1.00    4.00    --  111.00-111.00-150.00   61
 48  \w     84.00 109.00   1.00    4.00    --  111.00-111.00 120.00   25
 49  \w    131.00 178.00   1.00    4.00    --  111.00  77.00 -60.00   47
 50  \w    105.00 144.00   1.00    4.00    --  111.00  45.00  60.00   39
 51  \w     90.00 159.00   1.00    4.00    --  111.00  30.00 -90.00   69
 52  \w    128.00 174.00   1.00    4.00    --  111.00  30.00-180.00   46
 53  \w     42.00  84.00   1.00    1.00    --   41.65-153.00 149.00   42
 54  \w     -2.00  23.00   1.00    1.00    --   34.00  90.00-109.61   25
 55  \w     -1.00  24.00   1.00    1.00    --   34.00  88.00 141.92   25
 56  \w      6.00  31.00   1.00    1.00    --   38.00  79.00  30.49   25
 57  \w     -2.00  27.00   1.00    1.00    --  -41.65  19.00 -30.00   29
 58  \w   -115.00 -19.00   1.00    1.00    --  -41.65 -37.00-180.00   96
 59  \w    -85.00 -22.00   1.00    1.00    --  -41.65 -37.00 -60.00   63
 60  \w     14.00  39.00   1.00    1.00    --   46.00  78.00 -81.90   25
 61  \w     14.00  41.00   1.00    1.00    --   46.00  80.00 -14.79   27
 62  \w     14.00  39.00   1.00    1.00    --   46.00  80.00-161.81   25
 63  \w     14.00  39.00   1.00    1.00    --   46.00  81.00  78.74   25
 64  \w     15.00  40.00   1.00    1.00    --   46.00  76.00 164.37   25
 65  \w     31.00  58.00   1.00    1.00    --   58.00  71.00  28.85   27
 66  \w     34.00  60.00   1.00    1.00    --   58.00  69.00-127.33   26
 67  \w    101.00 127.00   1.00    1.00    --   58.00  69.00-127.33   26
 68  \w     28.00  54.00   1.00    1.00    --   58.00  71.00 172.93   26
 69  \w     32.00  58.00   1.00    1.00    --   62.00  71.00 -43.04   26
 70  \w     36.00  62.00   1.00    1.00    --   66.00  71.00  37.46   26
 71  \w     37.00  66.00   1.00    1.00    --   66.00  69.00 109.56   29
 72  \w     36.00  62.00   1.00    1.00    --   66.00  71.00-107.32   26
 73  \w    113.00 138.00   1.00    1.00    --   66.00  71.00  37.46   25
 74  \w     37.00  64.00   1.00    1.00    --   66.00  69.00  65.92   27
 75  \w     36.00  63.00   1.00    1.00    --   66.00  71.00 -20.23   27
 76  \w    104.00 130.00   1.00    1.00    --   70.00  71.00 178.93   26
 77  \w     40.00  66.00   1.00    1.00    --   70.00  71.00 178.93   26
 78  \w     45.00  76.00   1.00    1.00    --   74.00  67.00 152.56   31
 79  \w     44.00  70.00   1.00    1.00    --   74.00  71.00 -89.78   26
 80  \w     51.00  77.00   1.00    4.00    --   78.00  71.00 108.62   26
 81  \w     50.00  75.00   1.00    4.00    --   78.00  68.00 -65.49   25
 82  \w     49.00  78.00   1.00    4.00    --   78.00  69.00  66.03   29
 83  \w     51.00  77.00   1.00    4.00    --   78.00  60.00  32.21   26
 84  \w     52.00  78.00   1.00    4.00    --   82.00  71.00 -49.83   26
 85  \w     54.00  80.00   1.00    4.00    --   82.00  64.00-139.01   26
 86  \w     53.00  81.00   1.00    4.00    --   82.00  67.00  -1.62   28
 87  \w     53.00  79.00   1.00    4.00    --   82.00  70.00-172.63   26
 88  \w     58.00  84.00   1.00    4.00    --   86.00  65.00 155.26   26
 89  \w     62.00  90.00   1.00    4.00    --   90.00  62.00 -83.54   28
 90  \w     61.00  87.00   1.00    4.00    --   90.00  66.00-111.06   26
 91  \w     61.00 100.00   1.00    4.00    --   90.00  67.00  31.07   39
 92  \w     61.00 104.00   1.00    4.00    --   90.00  67.00  91.03   43
 93  \w     61.00  87.00   1.00    4.00    --   90.00  67.00-130.01   26
 94  \w     66.00  95.00   1.00    4.00    --   94.00  62.00 115.99   29
 95  \w     73.00  99.00   1.00    4.00    --  102.00  69.00 -47.63   26
 96  \w     78.00 104.00   1.00    4.00    --  106.00  65.00  20.11   26
 97  \w     78.00 110.00   1.00    4.00    --  106.00  61.00  92.17   32
 98  \w    120.00 165.00   1.00    4.00    --  111.00  70.00 -40.69   45
 99  \w     81.00 107.00   1.00    4.00    --  111.00  70.00 -40.69   26
100  \w    137.00 163.00   1.00    4.00    --  111.00  61.00-180.00   26
101  \w     83.00 118.00   1.00    4.00    --  111.00  61.00-180.00   35
102  \w     40.00  65.00   1.00    4.00    --  111.00 -45.00-150.00   25
103  \w     85.00 115.00   1.00    4.00    --  111.00  60.00-163.39   30
104  \w    116.00 142.00   1.00    4.00    --  111.00  63.00 132.66   26
105  \w    123.00 177.00   1.00    4.00    --  111.00  61.00  60.00   54
106  \w    140.00 166.00   1.00    4.00    --  111.00  61.00 150.00   26
107  \w     84.00 111.00   1.00    4.00    --  111.00  61.00 150.00   27
108  \w     83.00 110.00   1.00    4.00    --  111.00  63.00 132.66   27
109  \w     83.00 118.00   1.00    4.00    --  111.00  61.00  60.00   35
110  \w     40.00  65.00   1.00    4.00    --  111.00 -45.00 120.00   25
111  \w    150.00 176.00   1.00    4.00    --  111.00  70.00-110.43   26
112  \w     81.00 113.00   1.00    4.00    --  111.00  70.00-110.43   32
113  \w    135.00 177.00   1.00    4.00    --  111.00  70.00 -89.37   42
114  \w    153.00 178.00   1.00    4.00    --  111.00  61.00-120.00   25
115  \w     83.00 109.00   1.00    4.00    --  111.00  61.00-120.00   26
116  \w    147.00 173.00   1.00    4.00    --  111.00  61.00-150.00   26
117  \w    142.00 168.00   1.00    4.00    --  111.00  61.00 120.00   26
118  \w     83.00 110.00   1.00    4.00    --  111.00  61.00-150.00   27
119  \w     81.00 107.00   1.00    4.00    --  111.00  70.00 -89.37   26
120  \w     83.00 109.00   1.00    4.00    --  111.00  61.00 120.00   26
121  \w    119.00 162.00   1.00    4.00    --  111.00  45.00   0.00   43
122  \w    129.00 178.00   1.00    4.00    --  111.00  61.00   0.00   49
123  \w     89.00 116.00   1.00    4.00    --  111.00  45.00   0.00   27
124  \w    128.00 165.00   1.00    4.00    --  111.00  61.00  30.00   37
125  \w     83.00 121.00   1.00    4.00    --  111.00  61.00  30.00   38
126  \w     83.00 113.00   1.00    4.00    --  111.00  61.00   0.00   30
127  \w    135.00 161.00   1.00    4.00    --  111.00  61.00  90.00   26
128  \w     84.00 122.00   1.00    4.00    --  111.00  61.00  90.00   38
129  \w     82.00 109.00   1.00    4.00    --  111.00  70.00  93.12   27
130  \w    120.00 150.00   1.00    4.00    --  111.00  61.00 -60.00   30
131  \w     83.00 117.00   1.00    4.00    --  111.00  61.00 -60.00   34
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0490806000
_diffrn_orient_matrix_UB_12      -0.0125923000
_diffrn_orient_matrix_UB_13      0.0088813000
_diffrn_orient_matrix_UB_21      0.0085107000
_diffrn_orient_matrix_UB_22      -0.1228683000
_diffrn_orient_matrix_UB_23      0.0406957000
_diffrn_orient_matrix_UB_31      0.0055649000
_diffrn_orient_matrix_UB_32      0.0769716000
_diffrn_orient_matrix_UB_33      0.0664811000
_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  0.0348
_diffrn_reflns_av_unetI/netI     0.0117
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            86957
_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         76.500
_diffrn_reflns_theta_min         4.418
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.586
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64083
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.166
_exptl_crystal_description       plate
_exptl_crystal_F_000             2440
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.259
_refine_diff_density_min         -0.269
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     346
_refine_ls_number_reflns         6721
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0288
_refine_ls_R_factor_gt           0.0272
_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^)+(0.0437P)^2^+3.7829P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0751
_refine_ls_wR_factor_ref         0.0767
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6368
_reflns_number_total             6721
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00044k2.cif
_cod_data_source_block           071mhar23_auto
_cod_depositor_comments
'Adding full bibliography for 7718002--7718016.cif.'
_cod_database_code               7718004
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C53 H86 Ca2 N4 O2 Si4'
_shelx_estimated_absorpt_t_max   0.801
_shelx_estimated_absorpt_t_min   0.576
_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.a Ternary CH refined with riding coordinates:
 C26(H26), C23(H23), C14(H14), C11(H11)
2.b Aromatic/amide H refined with riding coordinates:
 C21(H21), C20(H20), C19(H19), C9(H9), C7(H7), C8(H8), C31(H31), C30(H30),
 C29(H29)
2.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C4(H4A,H4B,H4C),
 C25(H25A,H25B,H25C), C13(H13A,H13B,H13C), C16(H16A,H16B,H16C), C12(H12A,H12B,
 H12C), C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C24(H24A,H24B,H24C), C15(H15A,H15B,
 H15C)
;
_shelx_res_checksum              10351
_shelx_hkl_checksum              66638
_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 1.482
_oxdiff_exptl_absorpt_empirical_full_min 0.660