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_4124939
_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         '4(C35 H61 Lu O2 Si2)'
_chemical_formula_sum            'C140 H244 Lu4 O8 Si8'
_chemical_formula_weight         2979.94
_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   mixed
_atom_sites_solution_primary     heavy
_audit_creation_date             2015-03-25
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                69.3403(14)
_cell_angle_beta                 77.9753(14)
_cell_angle_gamma                89.5638(14)
_cell_formula_units_Z            1
_cell_length_a                   12.6449(10)
_cell_length_b                   14.3380(11)
_cell_length_c                   22.5972(18)
_cell_measurement_reflns_used    6231
_cell_measurement_temperature    100
_cell_measurement_theta_max      22.683
_cell_measurement_theta_min      2.163
_cell_volume                     3739.6(5)
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f 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  0.0663
_diffrn_reflns_av_unetI/netI     0.0727
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            41035
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.204
_diffrn_reflns_theta_min         0.987
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    2.730
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.5867
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0766 before and 0.0568 after correction.
The Ratio of minimum to maximum transmission is 0.7873.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.323
_exptl_crystal_description       block
_exptl_crystal_F_000             1544
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.07
_refine_diff_density_max         2.140
_refine_diff_density_min         -1.292
_refine_diff_density_rms         0.140
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.990
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     799
_refine_ls_number_reflns         13408
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      0.989
_refine_ls_R_factor_all          0.0665
_refine_ls_R_factor_gt           0.0427
_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^)+(0.0465P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0899
_refine_ls_wR_factor_ref         0.0989
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10096
_reflns_number_total             13408
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b00071_si_003.cif
_cod_data_source_block           mpc040_0m
_cod_depositor_comments
'Adding full bibliography for 4124937--4124939.cif.'
_cod_database_code               4124939
_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
 H2AA-C2A
 0.9 with sigma of 0.01
 H2AB-C2A
 0.9 with sigma of 0.01
 H2AC-C2A
 0.9 with sigma of 0.01
 H34A-C34A
 0.9 with sigma of 0.01
 H34C-C34A
 0.9 with sigma of 0.01
 H34B-C34A
 0.9 with sigma of 0.01
 H33A-C33B
 0.9 with sigma of 0.01
 C33B-H33B
 0.9 with sigma of 0.01
 H33C-C33B
 0.9 with sigma of 0.01
 C2B-H2BA
 0.9 with sigma of 0.01
 H2BC-C2B
 0.9 with sigma of 0.01
 H2BB-C2B
 0.9 with sigma of 0.01
 C33B-H33A
 0.9 with sigma of 0.01
 H33C-C33B
 0.9 with sigma of 0.01
 H33B-C33B
 0.9 with sigma of 0.01
 H2AB-C2A
 0.9 with sigma of 0.01
 H2AC-C2A
 0.9 with sigma of 0.01
 H2AA-C2A
 0.9 with sigma of 0.01
 C34A-H34A
 0.9 with sigma of 0.01
 H34C-C34A
 0.9 with sigma of 0.01
 H34B-C34A
 0.9 with sigma of 0.01
 H33A-C33B
 0.9 with sigma of 0.02
 H33B-C33B
 0.9 with sigma of 0.02
 H33C-C33B
 0.9 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uiso(H33A) = Uiso(H33C) = Uiso(H33B)
4.a Ternary CH refined with riding coordinates:
 C1A(H1A), C1B(H1B)
4.b Aromatic/amide H refined with riding coordinates:
 C29A(H29A), C28A(H28A), C26B(H26D), C30A(H30A), C10B(H10B), C25B(H25D),
 C11B(H11B), C12A(H12A), C12B(H12B), C24B(H24B), C10A(H10A), C11A(H11A)
4.c Idealised Me refined as rotating group:
 C21B(H21D,H21E,H21F), C17B(H17D,H17E,H17F), C7A(H7AA,H7AB,H7AC), C16B(H16D,
 H16E,H16F), C3A(H3AA,H3AB,H3AC), C7B(H7BA,H7BB,H7BC), C27A(H27A,H27B,H27C),
 C16A(H16A,H16B,H16C), C6B(H6BA,H6BB,H6BC), C15B(H15D,H15E,H15F), C20A(H20A,
 H20B,H20C), C4B(H4BA,H4BB,H4BC), C30B(H30B,H30C,H30D), C29B(H29B,H29C,H29D),
 C20B(H20D,H20E,H20F), C18B(H18A,H18B,H18C), C25A(H25A,H25B,H25C), C4A(H4AA,
 H4AB,H4AC), C37A(H37A,H37B,H37C), C31B(H31A,H31B,H31C), C17A(H17A,H17B,H17C),
 C6A(H6AA,H6AB,H6AC), C19A(H19A,H19B,H19C), C34B(H34D,H34E,H34F), C38A(H38A,
 H38B,H38C), C35B(H35A,H35B,H35C), C5B(H5BA,H5BB,H5BC), C3B(H3BA,H3BB,H3BC),
 C21A(H21A,H21B,H21C), C15A(H15A,H15B,H15C), C26A(H26A,H26B,H26C), C5A(H5AA,
 H5AB,H5AC)
;
_olex2_submission_special_instructions 'No special instructions were received'