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_7120566
_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(C16 H23 Y)'
_chemical_formula_sum            'C32 H46 Y2'
_chemical_formula_weight         608.51
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_symmetry_space_group_name_Hall  'P 2 2ab'
_symmetry_space_group_name_H-M   'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-07-18
_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
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.4805(4)
_cell_length_b                   15.4640(3)
_cell_length_c                   13.0556(2)
_cell_measurement_reflns_used    12242
_cell_measurement_temperature    150.02(10)
_cell_measurement_theta_max      26.1590
_cell_measurement_theta_min      3.4750
_cell_volume                     2923.49(11)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.02(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1428
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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    -94.00 -35.00   1.00   20.00    --  -17.77-178.00 -30.00   59
  2  \w    -89.00   7.00   1.00   20.00    --  -17.77 -37.00 -90.00   96
  3  \w     -8.00  88.00   1.00   20.00    --   18.70  77.00-120.00   96
  4  \w      5.00  88.00   1.00   20.00    --   18.70  57.00 150.00   83
  5  \w     -9.00  85.00   1.00   20.00    --   18.70  77.00  30.00   94
  6  \w      8.00  82.00   1.00   20.00    --   18.70-134.00-140.71   74
  7  \w    -50.00  16.00   1.00   20.00    --   18.70 -57.00   0.00   66
  8  \w    -46.00  37.00   1.00   20.00    --   18.70 -57.00-120.00   83
  9  \w     10.00  81.00   1.00   20.00    --   20.00-130.00  35.48   71
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0202720000
_diffrn_orient_matrix_UB_12      0.0338439000
_diffrn_orient_matrix_UB_13      0.0284171000
_diffrn_orient_matrix_UB_21      -0.0504155000
_diffrn_orient_matrix_UB_22      0.0137919000
_diffrn_orient_matrix_UB_23      0.0112722000
_diffrn_orient_matrix_UB_31      -0.0002526000
_diffrn_orient_matrix_UB_32      -0.0326137000
_diffrn_orient_matrix_UB_33      0.0341838000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0515
_diffrn_reflns_av_unetI/netI     0.0312
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            38521
_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         25.345
_diffrn_reflns_theta_min         3.370
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.967
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70621
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (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    1.383
_exptl_crystal_description       prism
_exptl_crystal_F_000             1264
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Toluene'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.985
_refine_diff_density_min         -0.876
_refine_diff_density_rms         0.085
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.45(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     359
_refine_ls_number_reflns         5363
_refine_ls_number_restraints     208
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0641
_refine_ls_R_factor_gt           0.0532
_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^)+(0.0463P)^2^+8.9183P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1213
_refine_ls_wR_factor_ref         0.1277
_reflns_Friedel_coverage         0.776
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                4688
_reflns_number_total             5363
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc05597h2.cif
_cod_data_source_block           aral305
_cod_database_code               7120566
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C16H23Y
_reflns_odcompleteness_completeness 99.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.55(2)
 0.45(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C27A-C32A = C32-C27
 1.55 with sigma of 0.02
4. Rigid bond restraints
 C28, C28, C28, C27, C27, C27, C27, C31, C31, C31, C30, C30, C30, C29, C29,
 C29, C29A, C29A, C29A, C28A, C28A, C28A, C27A, C27A, C27A, C27A, C31A, C31A,
 C31A, C30A, C30A, C30A, C32, C32, C32A, C32A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Uiso/Uaniso restraints and constraints
C28 \\sim C28 \\sim C28 \\sim C27 \\sim C27 \\sim C27 \\sim C27 \\sim C31 \\sim
C31 \\sim C31 \\sim C30 \\sim C30 \\sim C30 \\sim C29 \\sim C29 \\sim C29 \\sim
C29A \\sim C29A \\sim C29A \\sim C28A \\sim C28A \\sim C28A \\sim C27A \\sim
C27A \\sim C27A \\sim C27A \\sim C31A \\sim C31A \\sim C31A \\sim C30A \\sim
C30A \\sim C30A \\sim C32 \\sim C32 \\sim C32A \\sim C32A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02
6. Rigid body (RIGU) restrains
 Y2, Y2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(Y2A)=Sof(H17C)=Sof(H17D)=Sof(C29A)=Sof(H29A)=Sof(C28A)=Sof(H28A)=
 Sof(C27A)=Sof(C31A)=Sof(H31A)=Sof(C30A)=Sof(H30A)=Sof(C32A)=Sof(H32D)=
 Sof(H32E)=Sof(H32F)=1-FVAR(1)
 Sof(Y2)=Sof(H17A)=Sof(H17B)=Sof(C28)=Sof(H28)=Sof(C27)=Sof(C31)=Sof(H31)=
 Sof(C30)=Sof(H30)=Sof(C29)=Sof(H29)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=
 FVAR(1)
8.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C17(H17A,H17B), C17(H17C,H17D),
 C18(H18A,H18B), C19(H19A,H19B)
8.b Me refined with riding coordinates:
 C4(H4A,H4B,H4C), C10(H10A,H10B,H10C)
8.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C8(H8), C9(H9), C12(H12), C13(H13), C14(H14), C15(H15),
 C22(H22), C23(H23), C24(H24), C25(H25), C28(H28), C31(H31), C30(H30), C29(H29),
  C29A(H29A), C28A(H28A), C31A(H31A), C30A(H30A)
8.d Fitted pentagon refined as free rotating group:
 C28(C27,C31,C30,C29), C29A(C28A,C27A,C31A,C30A)
8.e Idealised Me refined as rotating group:
 C16(H16A,H16B,H16C), C20(H20A,H20B,H20C), C26(H26A,H26B,H26C), C32(H32A,H32B,
 H32C), C32A(H32D,H32E,H32F)
;
_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 1.792
_oxdiff_exptl_absorpt_empirical_full_min 0.637