X‒H Bond Activation on Cr(III),O Sites (X = R, H): Key Steps in Dehydrogenation and Hydrogenation Processes
Delley, Murielle F.; Silaghi, Marius-C.; Nuñez-Zarur, Francisco; Kovtunov, Kirill V.; Salnikov, Oleg G.; Estes, Deven P.; Koptyug, Igor V.; Comas-Vives, Aleix; Copéret, Christophe; Organometallics  (2016) –; doi:10.1021/acs.organomet.6b00744

data_4086884
_publ_section_title
;
 X--H Bond Activation on Cr(III),O Sites (X = R, H): Key Steps in
 Dehydrogenation and Hydrogenation Processes
;
_journal_name_full               Organometallics
_journal_paper_doi               10.1021/acs.organomet.6b00744
_journal_year                    2016
_chemical_formula_moiety         'C36 H84 Al3 Cr O12'
_chemical_formula_sum            'C36 H84 Al3 Cr O12'
_chemical_formula_weight         841.97
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_symmetry_space_group_name_Hall  'P 4nw 2abw'
_symmetry_space_group_name_H-M   'P 43 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-03-07
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3234(10)
_cell_length_b                   12.3234(10)
_cell_length_c                   31.719(3)
_cell_measurement_reflns_used    9925
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.96
_cell_measurement_theta_min      2.34
_cell_volume                     4817.0(7)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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_temperature      100(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0428
_diffrn_reflns_av_unetI/netI     0.0175
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            95783
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         28.420
_diffrn_reflns_theta_min         1.773
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.342
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.6157
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1232 before and 0.0576 after correction.
The Ratio of minimum to maximum transmission is 0.8257.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.161
_exptl_crystal_description       block
_exptl_crystal_F_000             1836
_exptl_crystal_recrystallization_method
'crystallization in pentane at -40 degree Celsius'
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.24
_refine_diff_density_max         0.429
_refine_diff_density_min         -1.306
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details
;
 Flack x determined using 2317 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.110(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.142
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     248
_refine_ls_number_reflns         6069
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.142
_refine_ls_R_factor_all          0.0411
_refine_ls_R_factor_gt           0.0386
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0695P)^2^+3.0866P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1257
_refine_ls_wR_factor_ref         0.1280
_reflns_Friedel_coverage         0.714
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                5773
_reflns_number_total             6069
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om6b00744_si_003.cif
_cod_data_source_block           fa-md194
_cod_original_cell_volume        4817.0(9)
_cod_database_code               4086884
_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.a Ternary CH refined with riding coordinates:
 C7(H7), C1(H1), C4(H4), C11(H11), C13(H13), C16(H16)
2.b Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C3(H3A,H3B,H3C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C12(H12A,
 H12B,H12C), C2(H2A,H2B,H2C), C6(H6A,H6B,H6C), C15(H15A,H15B,H15C), C10(H10A,
 H10B,H10C), C14(H14A,H14B,H14C), C18(H18A,H18B,H18C), C17(H17A,H17B,H17C)
;
_shelx_shelxl_version_number     2014/7
_olex2_exptl_crystal_mounting_method 'mounted in paratone oil'
_olex2_submission_special_instructions 'No special instructions were received'