Axial Ligand Coordination to the C-H Amination Catalyst Rh2(esp)2: A Structural and Spectroscopic Study.
Warzecha, Evan; Berto, Timothy C.; Berry, John F.; Inorganic chemistry 54 (2015) 8817–8824; doi:10.1021/acs.inorgchem.5b01532

data_4346446
_publ_section_title
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 Axial Ligand Coordination to the C-H Amination Catalyst Rh2(esp)2: A
 Structural and Spectroscopic Study.
;
_journal_issue                   17
_journal_name_full               'Inorganic chemistry'
_journal_page_first              8817
_journal_page_last               8824
_journal_paper_doi               10.1021/acs.inorgchem.5b01532
_journal_volume                  54
_journal_year                    2015
_chemical_formula_moiety
'2(C17 H24 O5 Rh), 0.87(C1 H2 Cl2), 0.13(C H4 O)'
_chemical_formula_sum            'C35 H50.25 Cl1.75 O10.13 Rh2'
_chemical_formula_weight         900.78
_chemical_name_common            'Compound 6'
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_cell_angle_alpha                100.665(6)
_cell_angle_beta                 91.507(6)
_cell_angle_gamma                115.278(4)
_cell_formula_units_Z            2
_cell_length_a                   11.6239(10)
_cell_length_b                   11.9813(8)
_cell_length_c                   15.6522(9)
_cell_measurement_reflns_used    9877
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      73.06
_cell_measurement_theta_min      4.18
_cell_volume                     1923.4(3)
_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, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.950
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0198
_diffrn_reflns_av_unetI/netI     0.0142
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            33048
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.950
_diffrn_reflns_theta_full        67.000
_diffrn_reflns_theta_max         73.073
_diffrn_reflns_theta_min         2.893
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    8.501
_exptl_absorpt_correction_T_max  0.6573
_exptl_absorpt_correction_T_min  0.0987
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0612 before and 0.0304 after correction.
The Ratio of minimum to maximum transmission is 0.1502.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'bluish green'
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.555
_exptl_crystal_description       block
_exptl_crystal_F_000             922
_exptl_crystal_size_max          0.564
_exptl_crystal_size_mid          0.213
_exptl_crystal_size_min          0.104
_refine_diff_density_max         0.567
_refine_diff_density_min         -0.414
_refine_diff_density_rms         0.060
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     471
_refine_ls_number_reflns         7332
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.125
_refine_ls_R_factor_all          0.0192
_refine_ls_R_factor_gt           0.0189
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0200P)^2^+1.6479P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0459
_refine_ls_wR_factor_ref         0.0461
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7243
_reflns_number_total             7332
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b01532_si_002.cif
_cod_data_source_block           berry543
_cod_original_cell_volume        1923.4(2)
_cod_database_code               4346446
_shelx_estimated_absorpt_t_max   0.472
_shelx_estimated_absorpt_t_min   0.086
_olex2_refinement_description
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1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Others
 Sof(O1S)=Sof(H1S)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(H2SC)=1-FVAR(1)
 Sof(Cl1S)=Sof(Cl2S)=Sof(C1S)=Sof(H1SA)=Sof(H1SB)=FVAR(1)
3.a Secondary CH2 refined with riding coordinates:
 C5A(H5AA,H5AB), C12A(H12A,H12B), C5(H5B,H5C), C12(H12C,H12D), C1S(H1SA,H1SB)
3.b Aromatic/amide H refined with riding coordinates:
 C7A(H7A), C8A(H8A), C9A(H9A), C11A(H11A), C7(H7), C8(H8), C9(H9), C11(H11)
3.c Idealised Me refined as rotating group:
 C3A(H3AA,H3AB,H3AC), C4A(H4AA,H4AB,H4AC), C14A(H14A,H14B,H14C), C15A(H15A,
 H15B,H15C), C17A(H17A,H17B,H17C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C14(H14D,
 H14E,H14F), C15(H15D,H15E,H15F), C17(H17D,H17E,H17F), C2S(H2SA,H2SB,H2SC)
3.d Idealised tetrahedral OH refined as rotating group:
 O1S(H1S)
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