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_7120563
_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 Dy)'
_chemical_formula_sum            'C32 H46 Dy2'
_chemical_formula_weight         755.69
_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     dual
_audit_creation_date             2017-07-03
_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                   14.4524(9)
_cell_length_b                   15.4426(6)
_cell_length_c                   13.0677(5)
_cell_measurement_reflns_used    7872
_cell_measurement_temperature    150.03(10)
_cell_measurement_theta_max      25.8010
_cell_measurement_theta_min      3.3880
_cell_volume                     2916.5(2)
_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      150.03(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0714
_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     57.00  87.00   1.00    1.20    --   18.86  57.00 -30.00   30
  2  \w    -54.00  58.00   1.00    1.20    --   18.86 -19.00 -60.00  112
  3  \w     17.00  50.00   1.00    1.20    --   18.86  57.00 -30.00   33
  4  \w    -37.00  -9.00   1.00    1.20    --  -17.77  57.00 -30.00   28
  5  \w    -19.00  45.00   1.00    1.20    --   18.86 -19.00-150.00   64
  6  \w    -38.00  30.00   1.00    1.20    --  -17.77  57.00-120.00   68
  7  \w    -21.00   7.00   1.00    1.20    --  -17.77 -77.00  30.00   28
  8  \w    -45.00  10.00   1.00    1.20    --  -17.77 -77.00 150.00   55
  9  \w     47.00  73.00   1.00    1.20    --   18.86-121.00   2.00   26
 10  \w    -11.00  15.00   1.00    1.20    --   18.86 -99.00-120.00   26
 11  \w     42.00  91.00   1.00    1.20    --   18.86 178.00-120.00   49
;
_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      0.0324433000
_diffrn_orient_matrix_UB_12      0.0352313000
_diffrn_orient_matrix_UB_13      0.0163751000
_diffrn_orient_matrix_UB_21      -0.0374583000
_diffrn_orient_matrix_UB_22      0.0337206000
_diffrn_orient_matrix_UB_23      -0.0104522000
_diffrn_orient_matrix_UB_31      -0.0221851000
_diffrn_orient_matrix_UB_32      -0.0053877000
_diffrn_orient_matrix_UB_33      0.0416208000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0702
_diffrn_reflns_av_unetI/netI     0.0775
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            28480
_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         26.390
_diffrn_reflns_theta_min         3.221
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    5.102
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66442
_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    1.721
_exptl_crystal_description       block
_exptl_crystal_F_000             1480
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Toluene'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         3.521
_refine_diff_density_min         -2.075
_refine_diff_density_rms         0.221
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.44(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.084
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     359
_refine_ls_number_reflns         5963
_refine_ls_number_restraints     260
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0898
_refine_ls_R_factor_gt           0.0728
_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^)+(0.0520P)^2^+46.1780P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1626
_refine_ls_wR_factor_ref         0.1727
_reflns_Friedel_coverage         0.783
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                4881
_reflns_number_total             5963
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cc05597h2.cif
_cod_data_source_block           '[(CpMe)2DyBu]2'
_cod_database_code               7120563
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C30H40Dy
_reflns_odcompleteness_completeness 99.61
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.56(8)
 0.44(8)
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
 C21-C26 = C21A-C26A
 1.55 with sigma of 0.02
4. Rigid bond restraints
 C1, C2, C3, C4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C17, C18, C19, C20
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C23A, C23A, C23A, C22A, C22A, C22A, C21A, C21A, C21A, C21A, C25A, C25A, C25A,
 C24A, C24A, C24A, C26A, C26A, C22, C22, C22, C21, C21, C21, C21, C25, C25, C25,
  C24, C24, C24, C23, C23, C23, C26, C26
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04
C17 \\sim C18 \\sim C19 \\sim C20: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04
C23A \\sim C23A \\sim C23A \\sim C22A \\sim C22A \\sim C22A \\sim C21A \\sim
C21A \\sim C21A \\sim C21A \\sim C25A \\sim C25A \\sim C25A \\sim C24A \\sim
C24A \\sim C24A \\sim C26A \\sim C26A \\sim C22 \\sim C22 \\sim C22 \\sim C21
\\sim C21 \\sim C21 \\sim C21 \\sim C25 \\sim C25 \\sim C25 \\sim C24 \\sim C24
\\sim C24 \\sim C23 \\sim C23 \\sim C23 \\sim C26 \\sim C26: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C32) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
6. Rigid body (RIGU) restrains
 Dy2A, Dy2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(Dy2A)=Sof(H17C)=Sof(H17D)=Sof(C23A)=Sof(H23A)=Sof(C22A)=Sof(H22A)=
 Sof(C21A)=Sof(C25A)=Sof(H25A)=Sof(C24A)=Sof(H24A)=Sof(C26A)=Sof(H26A)=
 Sof(H26B)=Sof(H26C)=1-FVAR(1)
 Sof(Dy2)=Sof(H17A)=Sof(H17B)=Sof(C22)=Sof(H22)=Sof(C21)=Sof(C25)=Sof(H25)=
 Sof(C24)=Sof(H24)=Sof(C23)=Sof(H23)=Sof(C26)=Sof(H26D)=Sof(H26E)=Sof(H26F)=
 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:
 C10(H10A,H10B,H10C), C26A(H26A,H26B,H26C)
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),
 C23A(H23A), C22A(H22A), C25A(H25A), C24A(H24A), C28(H28), C29(H29), C30(H30),
 C31(H31), C22(H22), C25(H25), C24(H24), C23(H23)
8.d Fitted pentagon refined as free rotating group:
 C23A(C22A,C21A,C25A,C24A), C22(C21,C25,C24,C23)
8.e Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C16(H16A,H16B,H16C), C20(H20A,H20B,H20C), C32(H32A,H32B,
 H32C), C26(H26D,H26E,H26F)
;
_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 1.415
_oxdiff_exptl_absorpt_empirical_full_min 0.738