Activation of C‒H bonds by rare-earth metallocene-butyl complexes
Layfield, Richard; Day, Benjamin M. Morgan; Guo, Fu-Sheng; Pugh, Thomas; Grindell, Richard; Chem. Commun.  (2017) –; doi:10.1039/C7CC05597H

data_7120560
_publ_section_title
;
 Activation of C--H bonds by rare-earth metallocene-butyl complexes
;
_journal_name_full               'Chem. Commun.'
_journal_paper_doi               10.1039/C7CC05597H
_journal_year                    2017
_chemical_formula_moiety         'C33 H37 N2 Y'
_chemical_formula_sum            'C33 H37 N2 Y'
_chemical_formula_weight         550.55
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-05-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2017-07-18 deposited with the CCDC.
2017-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.351(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.8886(16)
_cell_length_b                   14.8409(10)
_cell_length_c                   22.412(2)
_cell_measurement_reflns_used    5844
_cell_measurement_temperature    150.01(12)
_cell_measurement_theta_max      26.8050
_cell_measurement_theta_min      3.5940
_cell_volume                     5578.6(9)
_computing_cell_refinement       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(12)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0714
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -25.00  43.00   1.00    7.50    --   18.86 -37.00 -60.00   68
  2  \w     48.00  80.00   1.00    7.50    --   18.86  37.00-120.00   32
  3  \w     52.00  78.00   1.00    7.50    --   18.86  57.00-120.00   26
  4  \w      6.00  40.00   1.00    7.50    --   18.86  57.00-120.00   34
  5  \w     -6.00  22.00   1.00    7.50    --   18.86  37.00-120.00   28
  6  \w    -53.00  88.00   1.00    7.50    --   18.86   0.00-180.00  141
  7  \w     55.00  87.00   1.00    7.50    --   18.86-178.00 -90.00   32
  8  \w    -94.00 -38.00   1.00    7.50    --  -17.77-178.00  60.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0364052000
_diffrn_orient_matrix_UB_12      -0.0222656000
_diffrn_orient_matrix_UB_13      0.0034957000
_diffrn_orient_matrix_UB_21      -0.0111600000
_diffrn_orient_matrix_UB_22      -0.0026574000
_diffrn_orient_matrix_UB_23      -0.0335483000
_diffrn_orient_matrix_UB_31      0.0184768000
_diffrn_orient_matrix_UB_32      0.0422149000
_diffrn_orient_matrix_UB_33      -0.0002388000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.1094
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            10178
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         3.337
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.114
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.24527
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.27b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.311
_exptl_crystal_description       block
_exptl_crystal_F_000             2304
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Toluene'
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.15
_refine_diff_density_max         2.019
_refine_diff_density_min         -1.620
_refine_diff_density_rms         0.162
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.119
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     664
_refine_ls_number_reflns         10178
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.119
_refine_ls_R_factor_all          0.1318
_refine_ls_R_factor_gt           0.0922
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0001P)^2^+79.1563P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2118
_refine_ls_wR_factor_ref         0.2279
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6968
_reflns_number_total             10178
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc05597h2.cif
_cod_data_source_block           (CpMe)2Y(IMes')
_cod_original_cell_volume        5578.7(9)
_cod_database_code               7120560
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         Y1N2C33H37
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.725(3)
 0.275(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C30) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C43(H43A,H43B)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C8(H8), C15(H15), C17(H17), C23(H23), C24(H24),
 C25(H25), C26(H26), C29(H29), C30(H30), C31(H31), C32(H32), C35(H35), C36(H36),
  C39(H39), C41(H41), C48(H48), C50(H50), C56(H56), C57(H57), C58(H58),
 C59(H59), C62(H62), C63(H63), C64(H64), C65(H65)
4.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C19(H19A,H19B,H19C), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C), C27(H27A,H27B,H27C), C33(H33A,H33B,H33C), C44(H44A,
 H44B,H44C), C45(H45A,H45B,H45C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C),
 C54(H54A,H54B,H54C), C60(H60A,H60B,H60C), C66(H66A,H66B,H66C)
;
_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 3.055
_oxdiff_exptl_absorpt_empirical_full_min 0.546