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_7120565
_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         'C39 H45 Dy N2, C6 H6'
_chemical_formula_sum            'C45 H51 Dy N2'
_chemical_formula_weight         782.38
_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             2017-06-15
_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                 91.221(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.6469(6)
_cell_length_b                   12.9702(7)
_cell_length_c                   37.5845(12)
_cell_measurement_reflns_used    12690
_cell_measurement_temperature    150
_cell_measurement_theta_max      26.3410
_cell_measurement_theta_min      3.5370
_cell_volume                     7625.8(6)
_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_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1636
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.975
_diffrn_measured_fraction_theta_max 0.975
_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    -15.00  73.00   1.00    1.15    --   11.54  37.00 -60.00   88
  2  \w    -25.00  11.00   1.00    1.15    --  -12.00 -99.00-150.00   36
  3  \w    -44.00 -17.00   1.00    1.15    --  -12.00 -57.00-120.00   27
  4  \w    -65.00  38.00   1.00    1.15    --   11.54 -37.00 -60.00  103
  5  \w    -83.00 -50.00   1.00    1.15    --  -12.00   0.00-180.00   33
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0029092000
_diffrn_orient_matrix_UB_12      0.0461107000
_diffrn_orient_matrix_UB_13      -0.0101049000
_diffrn_orient_matrix_UB_21      -0.0006514000
_diffrn_orient_matrix_UB_22      0.0292398000
_diffrn_orient_matrix_UB_23      0.0159416000
_diffrn_orient_matrix_UB_31      0.0452355000
_diffrn_orient_matrix_UB_32      0.0033586000
_diffrn_orient_matrix_UB_33      -0.0000135000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0717
_diffrn_reflns_av_unetI/netI     0.0855
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            49837
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        25.348
_diffrn_reflns_theta_max         25.348
_diffrn_reflns_theta_min         3.248
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.992
_exptl_absorpt_correction_T_max  0.627
_exptl_absorpt_correction_T_min  0.487
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.27b (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
            model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.363
_exptl_crystal_description       prism
_exptl_crystal_F_000             3208
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Benzene'
_exptl_crystal_size_max          0.761
_exptl_crystal_size_mid          0.326
_exptl_crystal_size_min          0.287
_refine_diff_density_max         2.477
_refine_diff_density_min         -1.762
_refine_diff_density_rms         0.156
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.212
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     983
_refine_ls_number_reflns         13634
_refine_ls_number_restraints     662
_refine_ls_restrained_S_all      1.191
_refine_ls_R_factor_all          0.1168
_refine_ls_R_factor_gt           0.0893
_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^)+(0.0222P)^2^+95.2131P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1593
_refine_ls_wR_factor_ref         0.1705
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10461
_reflns_number_total             13634
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc05597h2.cif
_cod_data_source_block           (CpMe)3Dy(aIMes)
_cod_original_cell_volume        7625.8(5)
_cod_database_code               7120565
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         Dy1N2C51H57
_reflns_odcompleteness_completeness 96.42
_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
 C85, C89, C88, C90, C87, C86, C87A, C85A, C89A, C86A, C88A, C90A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C79, C81, C80, C82, C83, C84, C84A, C80A, C81A, C82A, C79A, C83A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C28, C32, C31, C30, C29, C33, C33A, C31A, C32A, C28A, C29A, C30A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C85 \\sim C89 \\sim C88 \\sim C90 \\sim C87 \\sim C86 \\sim C87A \\sim C85A
\\sim C89A \\sim C86A \\sim C88A \\sim C90A: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
C79 \\sim C81 \\sim C80 \\sim C82 \\sim C83 \\sim C84 \\sim C84A \\sim C80A
\\sim C81A \\sim C82A \\sim C79A \\sim C83A: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
C28 \\sim C32 \\sim C31 \\sim C30 \\sim C29 \\sim C33 \\sim C33A \\sim C31A
\\sim C32A \\sim C28A \\sim C29A \\sim C30A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C65) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C61, C65, C64, C63, C62
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C84A)=Sof(H84A)=Sof(C80A)=Sof(H80A)=Sof(C81A)=Sof(H81A)=Sof(C82A)=
 Sof(H82A)=Sof(C79A)=Sof(H79A)=Sof(C83A)=Sof(H83A)=1-FVAR(1)
 Sof(C79)=Sof(H79)=Sof(C81)=Sof(H81)=Sof(C80)=Sof(H80)=Sof(C82)=Sof(H82)=
 Sof(C83)=Sof(H83)=Sof(C84)=Sof(H84)=FVAR(1)
 Sof(C87A)=Sof(H87A)=Sof(C85A)=Sof(H85A)=Sof(C89A)=Sof(H89A)=Sof(C86A)=
 Sof(H86A)=Sof(C88A)=Sof(H88A)=Sof(C90A)=Sof(H90A)=1-FVAR(2)
 Sof(C85)=Sof(H85)=Sof(C89)=Sof(H89)=Sof(C88)=Sof(H88)=Sof(C90)=Sof(H90)=
 Sof(C87)=Sof(H87)=Sof(C86)=Sof(H86)=FVAR(2)
 Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=Sof(C28A)=Sof(C29A)=Sof(H29A)=
 Sof(C30A)=Sof(H30A)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=1-FVAR(3)
 Sof(C28)=Sof(C32)=Sof(H32)=Sof(C31)=Sof(H31)=Sof(C30)=Sof(H30)=Sof(C29)=
 Sof(H29)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=FVAR(3)
6.a 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), C32(H32), C31(H31), C30(H30), C29(H29), C31A(H31A),
 C32A(H32A), C29A(H29A), C30A(H30A), C35(H35), C36(H36), C37(H37), C38(H38),
 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), C79(H79), C81(H81), C80(H80), C82(H82), C83(H83),
  C84(H84), C84A(H84A), C80A(H80A), C81A(H81A), C82A(H82A), C79A(H79A),
 C83A(H83A), C85(H85), C89(H89), C88(H88), C90(H90), C87(H87), C86(H86),
 C87A(H87A), C85A(H85A), C89A(H89A), C86A(H86A), C88A(H88A), C90A(H90A)
6.b Fitted pentagon refined as free rotating group:
 C28(C32,C31,C30,C29), C31A(C32A,C28A,C29A,C30A)
6.c Fitted hexagon refined as free rotating group:
 C79(C81,C80,C82,C83,C84), C84A(C80A,C81A,C82A,C79A,C83A), C85(C89,C88,C90,C87,
 C86), C87A(C85A,C89A,C86A,C88A,C90A)
6.d 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), C33A(H33D,H33E,H33F), C39(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), C78(H78A,
 H78B,H78C)
;
_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 1.217
_oxdiff_exptl_absorpt_empirical_full_min 0.832