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_7120564
_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         '2(C39 H45 N2 Y), 2(C6 H6)'
_chemical_formula_sum            'C90 H102 N4 Y2'
_chemical_formula_weight         1417.57
_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             2017-05-30
_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                 90.982(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.5723(8)
_cell_length_b                   12.8913(8)
_cell_length_c                   37.4502(14)
_cell_measurement_reflns_used    6129
_cell_measurement_temperature    100.02(10)
_cell_measurement_theta_max      28.1280
_cell_measurement_theta_min      3.3410
_cell_volume                     7516.9(7)
_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      100.02(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0714
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -26.00  51.00   1.00    9.29    --  -17.77  57.00   0.00   77
  2  \w     33.00  59.00   1.00    9.29    --   18.86  77.00-120.00   26
  3  \w     61.00  89.00   1.00    9.29    --   18.86  77.00-120.00   28
  4  \w     50.00  90.00   1.00    9.29    --   18.86 178.00 -60.00   40
  5  \w      9.00  35.00   1.00    9.29    --   18.86  57.00-150.00   26
  6  \w     21.00  61.00   1.00    9.29    --   18.86 -99.00 -90.00   40
  7  \w    -93.00 -36.00   1.00    9.29    --  -17.77-178.00 -30.00   57
;
_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      0.0060794000
_diffrn_orient_matrix_UB_12      -0.0292165000
_diffrn_orient_matrix_UB_13      -0.0158119000
_diffrn_orient_matrix_UB_21      0.0087560000
_diffrn_orient_matrix_UB_22      -0.0448162000
_diffrn_orient_matrix_UB_23      0.0104322000
_diffrn_orient_matrix_UB_31      -0.0442732000
_diffrn_orient_matrix_UB_32      -0.0128734000
_diffrn_orient_matrix_UB_33      -0.0004294000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0677
_diffrn_reflns_av_unetI/netI     0.1093
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            37268
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         3.260
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.585
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77920
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.253
_exptl_crystal_description       block
_exptl_crystal_F_000             2992
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Benzene'
_exptl_crystal_size_max          0.49
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.15
_refine_diff_density_max         1.757
_refine_diff_density_min         -0.737
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     982
_refine_ls_number_reflns         13751
_refine_ls_number_restraints     350
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.1332
_refine_ls_R_factor_gt           0.0786
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0698P)^2^+23.7929P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1714
_refine_ls_wR_factor_ref         0.1962
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8792
_reflns_number_total             13751
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc05597h2.cif
_cod_data_source_block           (CpMe)3Y(aIMes)
_cod_database_code               7120564
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         Y1N2C40H45
_reflns_odcompleteness_completeness 99.70
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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. Rigid bond restraints
 C34A, C35A, C36A, C37A, C38A, C39A, C34, C35, C36, C37, C38, C39
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
3. Uiso/Uaniso restraints and constraints
C34A \\sim C35A \\sim C36A \\sim C37A \\sim C38A \\sim C39A \\sim C34 \\sim C35
\\sim C36 \\sim C37 \\sim C38 \\sim C39: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C86A, C87A, C88A, C89A, C90A, C85A, C86, C85, C90, C89, C88, C87
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C79A, C84A, C83A, C82A, C81A, C80A, C80, C79, C84, C83, C82, C81
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C34A)=Sof(C35A)=Sof(H35A)=Sof(C36A)=Sof(H36A)=Sof(C37A)=Sof(H37A)=
 Sof(C38A)=Sof(H38A)=Sof(C39A)=Sof(H39A)=Sof(H39B)=Sof(H39C)=1-FVAR(1)
 Sof(C34)=Sof(C35)=Sof(H35)=Sof(C36)=Sof(H36)=Sof(C37)=Sof(H37)=Sof(C38)=
 Sof(H38)=Sof(C39)=Sof(H39D)=Sof(H39E)=Sof(H39F)=FVAR(1)
 Sof(C86A)=Sof(H86A)=Sof(C87A)=Sof(H87A)=Sof(C88A)=Sof(H88A)=Sof(C89A)=
 Sof(H89A)=Sof(C90A)=Sof(H90A)=Sof(C85A)=Sof(H85A)=1-FVAR(2)
 Sof(C86)=Sof(H86)=Sof(C85)=Sof(H85)=Sof(C90)=Sof(H90)=Sof(C89)=Sof(H89)=
 Sof(C88)=Sof(H88)=Sof(C87)=Sof(H87)=FVAR(2)
 Sof(C79A)=Sof(H79A)=Sof(C84A)=Sof(H84A)=Sof(C83A)=Sof(H83A)=Sof(C82A)=
 Sof(H82A)=Sof(C81A)=Sof(H81A)=Sof(C80A)=Sof(H80A)=1-FVAR(3)
 Sof(C80)=Sof(H80)=Sof(C79)=Sof(H79)=Sof(C84)=Sof(H84)=Sof(C83)=Sof(H83)=
 Sof(C82)=Sof(H82)=Sof(C81)=Sof(H81)=FVAR(3)
6.a Me refined with riding coordinates:
 C78(H78A,H78B,H78C)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), 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), C35A(H35A),
 C36A(H36A), C37A(H37A), C38A(H38A), C40(H40), C42(H42), C45(H45), C47(H47),
 C54(H54), C56(H56), C62(H62), C63(H63), C64(H64), C65(H65), C68(H68), C69(H69),
  C70(H70), C71(H71), C74(H74), C75(H75), C76(H76), C77(H77), C35(H35),
 C36(H36), C37(H37), C38(H38), C79A(H79A), C84A(H84A), C83A(H83A), C82A(H82A),
 C81A(H81A), C80A(H80A), C80(H80), C79(H79), C84(H84), C83(H83), C82(H82),
 C81(H81), C86A(H86A), C87A(H87A), C88A(H88A), C89A(H89A), C90A(H90A),
 C85A(H85A), C86(H86), C85(H85), C90(H90), C89(H89), C88(H88), C87(H87)
6.c Fitted pentagon refined as free rotating group:
 C34A(C35A,C36A,C37A,C38A), C34(C35,C36,C37,C38)
6.d Fitted hexagon refined as free rotating group:
 C79A(C84A,C83A,C82A,C81A,C80A), C80(C79,C84,C83,C82,C81), C86A(C87A,C88A,C89A,
 C90A,C85A), C86(C85,C90,C89,C88,C87)
6.e Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), 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), C39A(H39A,H39B,H39C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C),
 C51(H51A,H51B,H51C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,
 H60C), C66(H66A,H66B,H66C), C72(H72A,H72B,H72C), C39(H39D,H39E,H39F)
;
_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 1.283
_oxdiff_exptl_absorpt_empirical_full_min 0.692