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_7718006
_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         'C68 H128 Ca2 K2 N6 O2 Si8, 0.5(C6 H6)'
_chemical_formula_sum            'C71 H131 Ca2 K2 N6 O2 Si8'
_chemical_formula_weight         1483.89
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-20
_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                88.998(2)
_cell_angle_beta                 80.120(2)
_cell_angle_gamma                75.017(3)
_cell_formula_units_Z            2
_cell_length_a                   11.5062(3)
_cell_length_b                   19.0448(6)
_cell_length_c                   20.7624(6)
_cell_measurement_reflns_used    19430
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      76.3260
_cell_measurement_theta_min      4.0980
_cell_volume                     4328.1(2)
_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 2014/5 (Sheldrick, 2014)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.980
_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   -121.00 -18.00   1.00    1.00    --  -41.40   0.00 -30.00  103
  2  \w    -41.00   7.00   1.00    1.00    --  -41.40  57.00 120.00   48
  3  \w     -2.00  25.00   1.00    1.00    --  -41.40  19.00-180.00   27
  4  \w    -40.00   7.00   1.00    1.00    --  -41.40  57.00 -60.00   47
  5  \w      7.00  45.00   1.00    1.00    --  -41.40   0.00 -30.00   38
  6  \w     30.00  86.00   1.00    1.00    --   41.40-125.00-120.00   56
  7  \w     30.00  89.00   1.00    1.00    --   41.40-125.00  60.00   59
  8  \w     80.00 177.00   1.00    3.14    --  111.00  15.00  90.00   97
  9  \w    114.00 141.00   1.00    3.14    --  111.00  77.00 120.00   27
 10  \w     34.00  74.00   1.00    3.14    --  111.00 -94.00-120.00   40
 11  \w     45.00  87.00   1.00    3.14    --  111.00 -94.00 -30.00   42
 12  \w     41.00  71.00   1.00    3.14    --  111.00 -45.00  90.00   30
 13  \w     41.00  68.00   1.00    3.14    --  111.00 -45.00-150.00   27
 14  \w    109.00 176.00   1.00    3.14    --  111.00  77.00 150.00   67
 15  \w     67.00 125.00   1.00    3.14    --  111.00  15.00 -90.00   58
 16  \w     40.00  71.00   1.00    3.14    --  111.00 -45.00 150.00   31
 17  \w     94.00 125.00   1.00    3.14    --  111.00 -77.00  30.00   31
 18  \w     75.00 109.00   1.00    3.14    --  111.00-111.00 -30.00   34
 19  \w    133.00 177.00   1.00    3.14    --  111.00  77.00  90.00   44
 20  \w     63.00 109.00   1.00    3.14    --  111.00-111.00  30.00   46
 21  \w     67.00 105.00   1.00    3.14    --  111.00-111.00-180.00   38
 22  \w    126.00 153.00   1.00    3.14    --  111.00  15.00 -90.00   27
 23  \w     40.00  90.00   1.00    3.14    --  111.00-111.00 -60.00   50
 24  \w     40.00  65.00   1.00    3.14    --  111.00 -45.00-120.00   25
 25  \w     43.00 105.00   1.00    3.14    --  111.00-111.00  90.00   62
 26  \w     67.00 109.00   1.00    3.14    --  111.00-111.00-150.00   42
 27  \w     91.00 178.00   1.00    3.14    --  111.00  30.00 -30.00   87
 28  \w     45.00  71.00   1.00    3.14    --  111.00 -45.00 -60.00   26
 29  \w     39.00  70.00   1.00    3.14    --  111.00-111.00 120.00   31
 30  \w     83.00 109.00   1.00    3.14    --  111.00-111.00 120.00   26
 31  \w     61.00  86.00   1.00    3.14    --  111.00 -61.00  90.00   25
 32  \w     42.00  70.00   1.00    3.14    --  111.00 -45.00  30.00   28
 33  \w     66.00 105.00   1.00    3.14    --  111.00-111.00  60.00   39
 34  \w     55.00  88.00   1.00    3.14    --  111.00 -61.00-120.00   33
 35  \w     80.00 108.00   1.00    3.14    --  111.00-111.00-120.00   28
 36  \w     96.00 149.00   1.00    3.14    --  111.00  45.00 120.00   53
 37  \w     42.00  72.00   1.00    3.14    --  111.00 -45.00 120.00   30
 38  \w     43.00 109.00   1.00    3.14    --  111.00-111.00 -90.00   66
 39  \w     86.00 126.00   1.00    3.14    --  111.00 178.00  90.00   40
 40  \w     58.00  83.00   1.00    3.14    --  111.00 -61.00  60.00   25
 41  \w     42.00  69.00   1.00    3.14    --  111.00 -77.00  30.00   27
 42  \w     -2.00  23.00   1.00    1.00    --   34.00  90.00  83.33   25
 43  \w      0.00  29.00   1.00    1.00    --   34.00  85.00-126.59   29
 44  \w     -4.00  35.00   1.00    1.00    --  -41.40  19.00 150.00   39
 45  \w    -43.00 -36.00   1.00    1.00    --  -41.40 -57.00  60.00    7
;
_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      -0.0705176000
_diffrn_orient_matrix_UB_12      -0.0590956000
_diffrn_orient_matrix_UB_13      0.0094532000
_diffrn_orient_matrix_UB_21      0.0029148000
_diffrn_orient_matrix_UB_22      -0.0036867000
_diffrn_orient_matrix_UB_23      -0.0743421000
_diffrn_orient_matrix_UB_31      0.1217441000
_diffrn_orient_matrix_UB_32      -0.0592607000
_diffrn_orient_matrix_UB_33      -0.0078085000
_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  0.0497
_diffrn_reflns_av_unetI/netI     0.0573
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            49068
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.597
_diffrn_reflns_theta_min         4.038
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.386
_exptl_absorpt_correction_T_max  0.820
_exptl_absorpt_correction_T_min  0.633
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.139
_exptl_crystal_description       block
_exptl_crystal_F_000             1610
_exptl_crystal_recrystallization_method
'Crystallised from concentrated benzene solution at room temperature'
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.485
_refine_diff_density_min         -0.374
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     883
_refine_ls_number_reflns         17878
_refine_ls_number_restraints     116
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0589
_refine_ls_R_factor_gt           0.0430
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0536P)^2^+1.0520P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1079
_refine_ls_wR_factor_ref         0.1228
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14246
_reflns_number_total             17878
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00044k2.cif
_cod_data_source_block           061ljm23
_cod_depositor_comments
'Adding full bibliography for 7718002--7718016.cif.'
_cod_database_code               7718006
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C89 H131 Ca2 N6 O2 Si8 K2'
_shelx_estimated_absorpt_t_max   0.687
_shelx_estimated_absorpt_t_min   0.537
_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
 C74-C69 = C71-C72 = C72-C73
 1.37 with sigma of 0.02
 C74-C73
 1.38 with sigma of 0.02
 C69-C70 = C70-C71
 1.36 with sigma of 0.02
 C74-C70 = C70-C72 = C71-C73
 2.37 with sigma of 0.04
 C74-C72
 2.38 with sigma of 0.04
 C69-C71
 2.36 with sigma of 0.04
 C74-C69 \\sim C69-C70 \\sim C70-C71 \\sim C71-C72 \\sim C72-C73 \\sim C73-C74
 with sigma of 0.02
 C74-C72 \\sim C74-C70 \\sim C72-C70 \\sim C71-C69 \\sim C71-C73 \\sim C73-C69
 with sigma of 0.04
3. Restrained planarity
 C69, C70, C71, C72, C73, C74
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 C69, C70, C71, C72, C73, C74
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C74, C69, C70, C71, C73, C72
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: C69(0.5) H69(0.5) C70(0.5) H70(0.5) C71(0.5) H71(0.5) C72(0.5)
 H72(0.5) C73(0.5) H73(0.5) C74(0.5) H74(0.5)
7.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C23(H23), C26(H26), C45(H45), C48(H48), C57(H57), C60(H60)
7.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C19(H19), C20(H20), C21(H21), C41(H41), C42(H42),
 C43(H43), C53(H53), C54(H54), C55(H55), C69(H69), C70(H70), C71(H71), C72(H72),
  C73(H73), C74(H74)
7.c Idealised Me refined as rotating group:
 C1(H1a,H1b,H1c), C2(H2a,H2b,H2c), C3(H3a,H3b,H3c), C4(H4a,H4b,H4c), C12(H12a,
 H12b,H12c), C13(H13a,H13b,H13c), C15(H15a,H15b,H15c), C16(H16a,H16b,H16c),
 C24(H24a,H24b,H24c), C25(H25a,H25b,H25c), C27(H27a,H27b,H27c), C28(H28a,H28b,
 H28c), C29(H29a,H29b,H29c), C30(H30a,H30b,H30c), C31(H31a,H31b,H31c), C32(H32a,
 H32b,H32c), C33(H33a,H33b,H33c), C34(H34a,H34b,H34c), C35(H35a,H35b,H35c),
 C36(H36a,H36b,H36c), C37(H37a,H37b,H37c), C38(H38a,H38b,H38c), C46(H46a,H46b,
 H46c), C47(H47a,H47b,H47c), C49(H49a,H49b,H49c), C50(H50a,H50b,H50c), C58(H58a,
 H58b,H58c), C59(H59a,H59b,H59c), C61(H61a,H61b,H61c), C62(H62a,H62b,H62c),
 C63(H63a,H63b,H63c), C64(H64a,H64b,H64c), C65(H65a,H65b,H65c), C66(H66a,H66b,
 H66c), C67(H67a,H67b,H67c), C68(H68a,H68b,H68c)
;
_shelx_res_checksum              8682
_shelx_hkl_checksum              10716
_ins_header
;
TITL 061ljm23 in P-1 
REM P-1 (#2 in standard setting)
CELL 1.54184  11.506203  19.044769  20.762445  88.9976  80.1201  75.0173
ZERR    2.00   0.000332   0.000610   0.000603   0.0025   0.0024   0.0026
LATT  1
SFAC C H N O Si K Ca
UNIT 178.00 262.00 12.00 4.00 16.00 4.00 4.00
REM  CrysAlisPro recorded range (K): Min=150.0; max=150.0; aver:150.0
TEMP -123
SIZE 0.12 0.16 0.21
TREF
HKLF 4
END
;
_olex2_exptl_crystal_mounting_method
'mounted on a MiTeGen MicroMount using perfluoropolyether oil and rapidly transferred to a goniometer head on a diffractometer fitted with an Oxford Cryostream open-flow nitrogen cooling device'
_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 1.257
_oxdiff_exptl_absorpt_empirical_full_min 0.758