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_4346445
_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         'C36 H46 N2 O8 Rh2, 2(C H2 Cl2)'
_chemical_formula_sum            'C38 H50 Cl4 N2 O8 Rh2'
_chemical_formula_weight         1010.42
_chemical_name_common            'Compound 5'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_cell_angle_alpha                90
_cell_angle_beta                 92.222(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.888(3)
_cell_length_b                   15.882(4)
_cell_length_c                   13.728(3)
_cell_measurement_reflns_used    9757
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      30.59
_cell_measurement_theta_min      2.43
_cell_volume                     2154.2(10)
_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 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0240
_diffrn_reflns_av_unetI/netI     0.0117
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            61124
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.587
_diffrn_reflns_theta_min         1.962
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.064
_exptl_absorpt_correction_T_max  0.7505
_exptl_absorpt_correction_T_min  0.4545
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1627 before and 0.0370 after correction.
The Ratio of minimum to maximum transmission is 0.6056.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.558
_exptl_crystal_description       plate
_exptl_crystal_F_000             1028
_exptl_crystal_size_max          0.342
_exptl_crystal_size_mid          0.232
_exptl_crystal_size_min          0.056
_refine_diff_density_max         0.590
_refine_diff_density_min         -0.525
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     297
_refine_ls_number_reflns         6618
_refine_ls_number_restraints     32
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0190
_refine_ls_R_factor_gt           0.0174
_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^)+(0.0202P)^2^+1.1890P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0426
_refine_ls_wR_factor_ref         0.0436
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6268
_reflns_number_total             6618
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b01532_si_002.cif
_cod_data_source_block           berry544
_cod_original_cell_volume        2154.4(10)
_cod_database_code               4346445
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.712
_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
2. Same fragment restrains
{C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A, C11A, C12A, C13A, C14A, C15A}
as
{C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15}
3. Others
 Sof(C2A)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=
 Sof(H4AC)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=
 Sof(H8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12C)=
 Sof(H12D)=Sof(C13A)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15A)=
 Sof(H15D)=Sof(H15E)=Sof(H15F)=1-FVAR(1)
 Sof(C2)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=
 Sof(H9)=Sof(C10)=Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(C13)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=
 FVAR(1)
 Uiso(C2A)=Uiso(C3A)=Uiso(C4A)=Uiso(C5A)=Uiso(C6A)=Uiso(C7A)=Uiso(C8A)=
 Uiso(C9A)=Uiso(C10A)=Uiso(C11A)=Uiso(C12A)=Uiso(C13A)=Uiso(C14A)=Uiso(C15A)=
 FVAR(2)
4.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C12(H12A,H12B), C5A(H5AA,H5AB), C12A(H12C,H12D), C1S(H1SA,H1SB)
4.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C11(H11), C7A(H7A), C8A(H8A), C9A(H9A), C11A(H11A)
4.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C14(H14A,H14B,H14C),
 C15(H15A,H15B,H15C), C3A(H3AA,H3AB,H3AC), C4A(H4AA,H4AB,H4AC), C14A(H14D,H14E,
 H14F), C15A(H15D,H15E,H15F)
;