Activation and functionalisation of carbon dioxide by bis-tris(pyrazolyl)borate-supported divalent samarium and trivalent lanthanide silylamide complexes.
Chowdhury, Tajrian; Wilson, Claire; Farnaby, Joy H.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 11884–11894; doi:10.1039/d4dt01382d

data_7716448
_publ_section_title
;
 Activation and functionalisation of carbon dioxide by
 bis-tris(pyrazolyl)borate-supported divalent samarium and trivalent
 lanthanide silylamide complexes.
;
_journal_issue                   28
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              11884
_journal_page_last               11894
_journal_paper_doi               10.1039/d4dt01382d
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C54 H69 B6 N36 O9 Sm5'
_chemical_formula_sum            'C54 H69 B6 N36 O9 Sm5'
_chemical_formula_weight         2183.06
_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
_audit_creation_date             2024-03-19
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-04-12 deposited with the CCDC.	2024-06-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.905(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.5313(5)
_cell_length_b                   39.6991(18)
_cell_length_c                   27.9152(10)
_cell_measurement_reflns_used    10186
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.2760
_cell_measurement_theta_min      2.7590
_cell_volume                     17618.8(12)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.871
_diffrn_measured_fraction_theta_max 0.826
_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     99.00 175.00   0.50   30.00    --  109.75  90.00  16.00  152
  2  \w     37.00  93.00   0.50   30.00    --  109.75 -90.00 -97.00  112
  3  \w     37.00  71.00   0.50   30.00    --  109.75 -77.00  90.00   68
  4  \w     37.00  71.00   0.50   30.00    --  109.75 -77.00 -30.00   68
  5  \w     37.00  93.00   0.50   30.00    --  109.75 -95.00 -30.00  112
  6  \w    104.00 132.00   0.50   30.00    --  109.75  15.00-180.00   56
  7  \w     37.00  71.00   0.50   30.00    --  109.75 -77.00-120.00   68
  8  \w     37.00  93.00   0.50   30.00    --  109.75 -95.00  90.00  112
  9  \w    104.00 132.00   0.50   30.00    --  109.75  15.00 150.00   56
 10  \w     37.00  71.00   0.50   30.00    --  109.75 -77.00  30.00   68
 11  \w     37.00  71.00   0.50   30.00    --  109.75 -77.00  60.00   68
 12  \w    104.00 132.00   0.50   30.00    --  109.75  15.00   0.00   56
 13  \w    -13.00  71.00   0.50    5.00    --   45.30 -90.00 -97.00  168
 14  \w    -27.00  41.00   0.50    5.00    --   45.30 -57.00 -90.00  136
 15  \w    -30.00  15.00   0.50    5.00    --   45.30 -38.00 150.00   90
 16  \w    -30.00  15.00   0.50    5.00    --   45.30 -38.00-180.00   90
 17  \w     39.00 123.00   0.50    5.00    --   45.30  19.00 120.00  168
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0128281000
_diffrn_orient_matrix_UB_12      0.0268025000
_diffrn_orient_matrix_UB_13      -0.0370774000
_diffrn_orient_matrix_UB_21      0.0646104000
_diffrn_orient_matrix_UB_22      -0.0229524000
_diffrn_orient_matrix_UB_23      -0.0145073000
_diffrn_orient_matrix_UB_31      -0.0712732000
_diffrn_orient_matrix_UB_32      -0.0160985000
_diffrn_orient_matrix_UB_33      -0.0412484000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.2366
_diffrn_reflns_av_unetI/netI     0.2176
_diffrn_reflns_Laue_measured_fraction_full 0.871
_diffrn_reflns_Laue_measured_fraction_max 0.826
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       49
_diffrn_reflns_limit_k_min       -46
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            87712
_diffrn_reflns_point_group_measured_fraction_full 0.871
_diffrn_reflns_point_group_measured_fraction_max 0.826
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         77.933
_diffrn_reflns_theta_min         2.768
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    25.160
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45149
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
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    1.646
_exptl_crystal_description       plate
_exptl_crystal_F_000             8456
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.015
_refine_diff_density_max         8.552
_refine_diff_density_min         -4.530
_refine_diff_density_rms         0.615
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.389
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     931
_refine_ls_number_reflns         31093
_refine_ls_number_restraints     2640
_refine_ls_restrained_S_all      1.336
_refine_ls_R_factor_all          0.2706
_refine_ls_R_factor_gt           0.1792
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4017
_refine_ls_wR_factor_ref         0.4614
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16092
_reflns_number_total             31093
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt01382d2.cif
_cod_data_source_block           4_Sm_Sm5Tp6_u_OH9
_cod_depositor_comments
'Adding full bibliography for 7716442--7716448.cif.'
_cod_database_code               7716448
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_usercomment     'TC 10_9b Sm(Tp)2(u-OH)_x2_hex'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups
 At 1.5 times of:
  All O(H) groups
2. Restrained distances
 C101-C100 \\sim C102-C101 \\sim C98-C97 \\sim C99-C98 \\sim C93-C92 \\sim
C92-C91 \\sim C74-C73 \\sim C75-
 C74 \\sim C80-C79 \\sim C81-C80 \\sim C68-C67 \\sim C69-C68 \\sim C71-C70
\\sim C72-C71 \\sim C66-C65 ~
 C65-C64 \\sim C77-C76 \\sim C78-C77 \\sim C95-C94 \\sim C96-C95 \\sim
C107-C106 \\sim C108-C107 \\sim C62-
 C61 \\sim C63-C62 \\sim C104-C103 \\sim C105-C104 \\sim C56-C55 \\sim C57-C56
\\sim C89-C88 \\sim C90-C89
 \\sim C83-C82 \\sim C84-C83 \\sim C86-C85 \\sim C87-C86
 with sigma of 0.02
 N40-C60 \\sim N39-C58 \\sim N48-C72 \\sim N47-C70 \\sim N46-C69 \\sim N45-C67
\\sim N44-C66 \\sim N43-C64
 \\sim N52-C78 \\sim N51-C76 \\sim N50-C75 \\sim N49-C73 \\sim N54-C81 \\sim
N53-C79 \\sim N37-C55 \\sim N38-
 C57 \\sim N42-C63 \\sim N41-C61 \\sim N71-C106 \\sim N72-C108 \\sim N67-C100
\\sim N68-C102 \\sim N59-C88
 \\sim N60-C90 \\sim N69-C103 \\sim N70-C105 \\sim N63-C94 \\sim N64-C96 \\sim
N65-C97 \\sim N66-C99 \\sim N61-
 C91 \\sim N62-C93 \\sim N57-C85 \\sim N58-C87 \\sim N55-C82 \\sim N56-C84
 with sigma of 0.02
 N64-N63 \\sim N66-N65 \\sim N62-N61 \\sim N72-N71 \\sim N70-N69 \\sim N68-N67
\\sim N60-N59 \\sim N58-N57
 \\sim N56-N55 \\sim N50-N49 \\sim N54-N53 \\sim N52-N51 \\sim N46-N45 \\sim
N48-N47 \\sim N44-N43
 with sigma of 0.02
 C39-C38 \\sim C38-C37 \\sim C20-C19 \\sim C21-C20 \\sim C41-C40 \\sim C42-C41
\\sim C44-C43 \\sim C45-C44
 \\sim C53-C52 \\sim C54-C53 \\sim C48-C47 \\sim C47-C46 \\sim C9-C8 \\sim
C8-C7 \\sim C6-C5 \\sim C5-C4 \\sim C23-
 C22 \\sim C24-C23 \\sim C27-C26 \\sim C26-C25 \\sim C15-C14 \\sim C14-C13
\\sim C12-C11 \\sim C11-C10 ~
 C50-C49 \\sim C51-C50 \\sim C35-C34 \\sim C36-C35 \\sim C30-C29 \\sim C29-C28
\\sim C33-C32 \\sim C32-C31
 \\sim C18-C17 \\sim C17-C16 \\sim C2-C1 \\sim C3-C2
 with sigma of 0.02
 N30-C45 \\sim N29-C43 \\sim N27-C40 \\sim N28-C42 \\sim N26-C39 \\sim N25-C37
\\sim N13-C19 \\sim N14-C21
 \\sim N31-C46 \\sim N32-C48 \\sim N19-C28 \\sim N20-C30 \\sim N24-C36 \\sim
N23-C34 \\sim N34-C51 \\sim N33-
 C49 \\sim N12-C18 \\sim N11-C16 \\sim N17-C25 \\sim N18-C27 \\sim N15-C22
\\sim N16-C24 \\sim N22-C33 ~
 N21-C31 \\sim N8-C12 \\sim N7-C10 \\sim N10-C15 \\sim N9-C13 \\sim N6-C9 \\sim
N5-C7 \\sim N4-C6 \\sim N3-C4 ~
 N2-C3 \\sim N1-C1
 with sigma of 0.02
 N8-N7 \\sim N12-N11 \\sim N9-N10 \\sim N4-N3 \\sim N6-N5 \\sim N2-N1 \\sim
N20-N19 \\sim N22-N21 \\sim N24-
 N23 \\sim N28-N27 \\sim N26-N25 \\sim N30-N29 \\sim N14-N13 \\sim N16-N15
\\sim N18-N17 \\sim N32-N31 ~
 N36-N35 \\sim N34-N33
 with sigma of 0.02
3.a Ternary CH refined with riding coordinates:
 O5(H5), O7(H7), O14(H14A), O15(H15A), B1(H1A), B2(H2A), B3(H3A), B4(H4A),
 B5(H5B), B6(H6A), B7(H7B), B8(H8A), B9(H9A), B10(H10A), B11(H11A), B12(H12A)
3.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5A), C6(H6), C7(H7A), C8(H8), C9(H9),
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17),
  C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24),
 C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32),
  C33(H33), C34(H34), C35(H35), C36(H36), C37(H37), C38(H38), C39(H39),
 C40(H40), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C47(H47),
  C48(H48), C49(H49), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54),
 C55(H55), C56(H56), C57(H57), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62),
  C63(H63), C64(H64), C65(H65), C66(H66), C67(H67), C68(H68), C69(H69),
 C70(H70), C71(H71), C72(H72), C73(H73), C74(H74), C75(H75), C76(H76), C77(H77),
  C78(H78), C79(H79), C80(H80), C81(H81), C82(H82), C83(H83), C84(H84),
 C85(H85), C86(H86), C87(H87), C88(H88), C89(H89), C90(H90), C91(H91), C92(H92),
  C93(H93), C94(H94), C95(H95), C96(H96), C97(H97), C98(H98), C99(H99),
 C100(H100), C101(H101), C102(H102), C103(H103), C104(H104), C105(H105),
 C106(H106), C107(H107), C108(H108)
;
_shelx_res_checksum              2108
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 3.972
_oxdiff_exptl_absorpt_empirical_full_min 0.332