The Nature of Secondary Interactions at Electrophilic Metal Sites of Molecular and Silica-Supported Organolutetium Complexes from Solid-State NMR Spectroscopy.
Conley, Matthew P.; Lapadula, Giuseppe; Sanders, Kevin; Gajan, David; Lesage, Anne; Del Rosal, Iker; Maron, Laurent; Lukens, Wayne W.; Copéret, Christophe; Andersen, Richard A.; Journal of the American Chemical Society 138 (2016) 3831–3843; doi:10.1021/jacs.6b00071

data_4124937
_publ_section_title
;
 The Nature of Secondary Interactions at Electrophilic Metal Sites of
 Molecular and Silica-Supported Organolutetium Complexes from Solid-State
 NMR Spectroscopy.
;
_journal_issue                   11
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              3831
_journal_page_last               3843
_journal_paper_doi               10.1021/jacs.6b00071
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         'C28 H59 Lu O Si4'
_chemical_formula_sum            'C28 H59 Lu O Si4'
_chemical_formula_weight         699.08
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-03-26
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                89.663(4)
_cell_angle_beta                 89.314(3)
_cell_angle_gamma                89.923(3)
_cell_formula_units_Z            4
_cell_length_a                   12.8020(15)
_cell_length_b                   13.5388(15)
_cell_length_c                   20.551(2)
_cell_measurement_reflns_used    9437
_cell_measurement_temperature    100
_cell_measurement_theta_max      34.060
_cell_measurement_theta_min      2.391
_cell_volume                     3561.7(7)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.952
_diffrn_measured_fraction_theta_max 0.953
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART Apex2'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0385
_diffrn_reflns_av_unetI/netI     0.0416
_diffrn_reflns_Laue_measured_fraction_full 0.952
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            43732
_diffrn_reflns_point_group_measured_fraction_full 0.952
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         2.191
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.924
_exptl_absorpt_correction_T_max  0.7468
_exptl_absorpt_correction_T_min  0.5514
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0873 before and 0.0689 after correction.
The Ratio of minimum to maximum transmission is 0.7384.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear light white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.304
_exptl_crystal_description       block
_exptl_crystal_F_000             1448
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.476
_refine_diff_density_min         -2.784
_refine_diff_density_rms         0.221
_refine_ls_extinction_coef       0.00017(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.198
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     642
_refine_ls_number_reflns         13877
_refine_ls_number_restraints     17
_refine_ls_restrained_S_all      1.198
_refine_ls_R_factor_all          0.1059
_refine_ls_R_factor_gt           0.0801
_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^)+98.2542P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1761
_refine_ls_wR_factor_ref         0.1925
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10400
_reflns_number_total             13877
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b00071_si_002.cif
_cod_data_source_block           micha_p_1
_cod_depositor_comments
'Adding full bibliography for 4124937--4124939.cif.'
_cod_original_cell_volume        3561.6(7)
_cod_database_code               4124937
_shelxl_version_number           2014-3
_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
 C23A-C21A
 1.45 with sigma of 0.02
 C6BB-Si11
 1.7 with sigma of 0.02
 Si2B-C2BB \\sim Si2B-C4BA \\sim Si2B-C3BB
 with sigma of 0.001
 C2BB-C4BA \\sim C2BB-C3BB \\sim C4BA-C3BB
 with sigma of 0.001
 C5BB-C6BB \\sim C5BB-C7BB \\sim C6BB-C7BB
 with sigma of 0.001
 C1BA-C5BB \\sim C1BA-C6BB \\sim C1BA-C7BB
 with sigma of 0.001
 Si1B-C5BB \\sim Si1B-C6BB \\sim Si1B-C7BB
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
Uanis(C1BB) = Uanis(C1BA)
Uanis(C7A) = Uanis(C6A) = Uanis(C5A)
Uanis(Si2B) = Uanis(Si22)
Uanis(Si1B) = Uanis(Si11)
Uanis(C4BB) = Uanis(C9B) = Uanis(C2BA)
Uanis(C2BB) = Uanis(C3BB) = Uanis(C4BA)
Uanis(C3B) = Uanis(C3BB) = Uanis(C4BA) = Uanis(C4BB) = Uanis(C2BA) = Uanis(C2BB)
Uanis(C7B) = Uanis(C7BB) = Uanis(C6B) = Uanis(C5B) = Uanis(C5BB) = Uanis(C6BB)
Uanis(C7BB) = Uanis(C7B) = Uanis(C5BB) = Uanis(C5B) = Uanis(C6BB) = Uanis(C6B)
Uanis(C3B) = Uanis(C3BB) = Uanis(C4BA) = Uanis(C4BB) = Uanis(C2BA) = Uanis(C2BB)
4. Others
 Sof(C1BA)=Sof(H1BA)=Sof(C2BB)=Sof(H2BD)=Sof(H2BE)=Sof(H2BF)=Sof(C4BA)=
 Sof(H4BA)=Sof(H4BB)=Sof(H4BC)=Sof(Si22)=Sof(Si11)=Sof(C5BB)=Sof(H5BD)=
 Sof(H5BE)=Sof(H5BF)=Sof(C6BB)=Sof(H6BD)=Sof(H6BE)=Sof(H6BF)=Sof(C7BB)=
 Sof(H7BD)=Sof(H7BE)=Sof(H7BF)=Sof(C3BB)=Sof(H3BD)=Sof(H3BE)=Sof(H3BF)=1-FVAR(1)
 Sof(Si1B)=Sof(Si2B)=Sof(C2BA)=Sof(H2BA)=Sof(H2BB)=Sof(H2BC)=Sof(C3B)=
 Sof(H3BA)=Sof(H3BB)=Sof(H3BC)=Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(H5BC)=Sof(C6B)=
 Sof(H6BA)=Sof(H6BB)=Sof(H6BC)=Sof(C7B)=Sof(H7BA)=Sof(H7BB)=Sof(H7BC)=Sof(C1BB)=
 Sof(H1BB)=Sof(C4BB)=Sof(H4BD)=Sof(H4BE)=Sof(H4BF)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C1A(H1A), C8A(H8A), C8B(H8B), C1BA(H1BA), C1BB(H1BB)
5.b Aromatic/amide H refined with riding coordinates:
 C19A(H19A), C18A(H18A), C17B(H17B), C18B(H18B), C17A(H17A), C19B(H19B)
5.c Idealised Me refined as rotating group:
 C9B(H9BA,H9BB,H9BC), C2A(H2AA,H2AB,H2AC), C26A(H26D,H26E,H26F), C9A(H9AA,H9AB,
 H9AC), C11A(H11D,H11E,H11F), C10A(H10D,H10E,H10F), C3A(H3AA,H3AB,H3AC),
 C27A(H27D,H27E,H27F), C28A(H28D,H28E,H28F), C24A(H24D,H24E,H24F), C23A(H23D,
 H23E,H23F), C22A(H22D,H22E,H22F), C12A(H12D,H12E,H12F), C14A(H14D,H14E,H14F),
 C4A(H4AA,H4AB,H4AC), C13A(H13D,H13E,H13F), C10B(H10A,H10B,H10C), C11B(H11A,
 H11B,H11C), C22B(H22A,H22B,H22C), C26B(H26A,H26B,H26C), C23B(H23A,H23B,H23C),
 C14B(H14A,H14B,H14C), C27B(H27A,H27B,H27C), C13B(H13A,H13B,H13C), C24B(H24A,
 H24B,H24C), C28B(H28A,H28B,H28C), C12B(H12A,H12B,H12C), C2BA(H2BA,H2BB,H2BC),
 C3B(H3BA,H3BB,H3BC), C5B(H5BA,H5BB,H5BC), C6B(H6BA,H6BB,H6BC), C7B(H7BA,H7BB,
 H7BC), C2BB(H2BD,H2BE,H2BF), C4BA(H4BA,H4BB,H4BC), C5BB(H5BD,H5BE,H5BF),
 C6BB(H6BD,H6BE,H6BF), C7BB(H7BD,H7BE,H7BF), C3BB(H3BD,H3BE,H3BF), C7A(H7AA,
 H7AB,H7AC), C6A(H6AA,H6AB,H6AC), C5A(H5AA,H5AB,H5AC), C4BB(H4BD,H4BE,H4BF)
;
_olex2_submission_special_instructions 'No special instructions were received'