CO methylenation mediated by organo-alkali metal reagents: metal identity and ligand effects
Yang, Xiao; Davison, Nathan; Lowe, Matthew E.; Waddell, Paul G.; Armstrong, Roly J.; McMullin, Claire L.; Hopkinson, Matthew N.; Lu, Erli; Chemical Science 16 (2025) 11151–11160; doi:10.1039/D5SC02313K

data_1574667
_publ_section_title
;
 C&#xE001;O methylenation mediated by organo-alkali metal reagents: metal
 identity and ligand effects
;
_journal_issue                   24
_journal_name_full               'Chemical Science'
_journal_page_first              11151
_journal_page_last               11160
_journal_paper_doi               10.1039/D5SC02313K
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C12 H36 K4 O4 Si4'
_chemical_formula_sum            'C12 H36 K4 O4 Si4'
_chemical_formula_weight         513.17
_space_group_crystal_system      cubic
_space_group_IT_number           219
_space_group_name_Hall           'F -4a 2 3'
_space_group_name_H-M_alt        'F -4 3 c'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-03-28
_audit_creation_method
;
Olex2 1.5-ac5-023
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2024-07-30 deposited with the CCDC.	2025-05-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.5314(3)
_cell_length_b                   17.5314(3)
_cell_length_c                   17.5314(3)
_cell_measurement_reflns_used    1301
_cell_measurement_temperature    150.0(2)
_cell_measurement_theta_max      73.4420
_cell_measurement_theta_min      5.0320
_cell_volume                     5388.28(16)
_computing_cell_refinement       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5-ac5-023 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-023 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.0(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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   -118.00 -83.00   0.50    0.10    --  -95.69-112.00  49.00   70
  2  \w    -35.00 -10.00   0.50    0.10    --  -95.69  30.00   0.00   50
  3  \w     12.00  39.00   0.50    0.10    --  -39.19  19.00  30.00   54
  4  \w    -23.00  10.00   0.50    0.10    --  -39.19  19.00  30.00   66
  5  \w     37.00  62.00   0.50    0.10    --  110.26 -74.00-118.00   50
  6  \w     67.00  93.00   0.50    0.10    --  110.26 -74.00-118.00   52
  7  \w     24.00  49.00   0.50    0.10    --  110.26 -45.00-120.00   50
  8  \w     25.00  59.00   0.50    0.10    --  102.48-102.00 176.00   68
  9  \w    -13.00  37.00   0.50    0.10    --  -39.19  19.00 -90.00  100
 10  \w      6.00  41.00   0.50    0.10    --  -39.19  19.00  60.00   70
 11  \w    -35.00 -10.00   0.50    0.10    --  -95.69  30.00 120.00   50
 12  \w     63.00 105.00   0.50    0.10    --  102.48-102.00 176.00   84
 13  \w     23.00  48.00   0.50    0.10    --  110.26 -45.00 -60.00   50
 14  \w     23.00  48.00   0.50    0.10    --  110.26 -45.00  30.00   50
 15  \w     23.00  48.00   0.50    0.10    --  110.26 -45.00 -90.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0851545796
_diffrn_orient_matrix_UB_12      0.0074305619
_diffrn_orient_matrix_UB_13      -0.0204351776
_diffrn_orient_matrix_UB_21      0.0031271695
_diffrn_orient_matrix_UB_22      -0.0859283918
_diffrn_orient_matrix_UB_23      -0.0182075719
_diffrn_orient_matrix_UB_31      -0.0215834081
_diffrn_orient_matrix_UB_32      0.0168908361
_diffrn_orient_matrix_UB_33      -0.0834601953
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0270
_diffrn_reflns_av_unetI/netI     0.0245
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            2632
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.412
_diffrn_reflns_theta_min         5.046
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.691
_exptl_absorpt_correction_T_max  0.367
_exptl_absorpt_correction_T_min  0.138
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.73a (Rigaku Oxford Diffraction, 2022)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.265
_exptl_crystal_description       block
_exptl_crystal_F_000             2176
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.156
_refine_diff_density_min         -0.143
_refine_diff_density_rms         0.033
_refine_ls_abs_structure_details
;
 Flack x determined using 171 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.026(16)
_refine_ls_extinction_coef       0.00012(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/1 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.120
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     21
_refine_ls_number_reflns         458
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.120
_refine_ls_R_factor_all          0.0194
_refine_ls_R_factor_gt           0.0185
_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^)+(0.0233P)^2^+2.2526P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0510
_refine_ls_wR_factor_ref         0.0517
_reflns_Friedel_coverage         0.768
_reflns_Friedel_fraction_full    0.989
_reflns_Friedel_fraction_max     0.971
_reflns_number_gt                418
_reflns_number_total             458
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02313k2.cif
_cod_data_source_block           elu230011_off_fa
_cod_depositor_comments
'Adding full bibliography for 1574667--1574668.cif.'
_cod_original_cell_volume        5388.3(3)
_cod_original_sg_symbol_Hall     'F -4c 2 3'
_cod_database_code               1574667
_chemical_oxdiff_formula         'C1 H3 O1 Si1 K1'
_shelx_estimated_absorpt_t_max   0.513
_shelx_estimated_absorpt_t_min   0.308
_diffrn_oxdiff_digest_frames
;
019b73ea15aed98d30bf58b3a7a573159600914f94e
;
_diffrn_oxdiff_digest_hkl
;
013bcee078d35fb294baa8267b1e41941f9fa5
;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2.a Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              73182
_shelx_shelxl_version_number     2019/1
_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 1.461
_oxdiff_exptl_absorpt_empirical_full_min 0.630