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_4346444
_publ_section_title
;
 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(C23 H29 N O4 Rh)'
_chemical_formula_sum            'C46 H58 N2 O8 Rh2'
_chemical_formula_weight         972.76
_chemical_name_common            'Compound 4'
_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   geom
_atom_sites_solution_primary     direct
_cell_angle_alpha                83.808(11)
_cell_angle_beta                 85.788(9)
_cell_angle_gamma                77.087(9)
_cell_formula_units_Z            2
_cell_length_a                   10.828(3)
_cell_length_b                   11.342(3)
_cell_length_c                   18.180(4)
_cell_measurement_reflns_used    9914
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      27.41
_cell_measurement_theta_min      2.26
_cell_volume                     2160.7(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 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  Gromit
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0383
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            19328
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         1.128
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.819
_exptl_absorpt_correction_T_max  1
_exptl_absorpt_correction_T_min  0.336181
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.0778 before and 0.0552 after correction.
 The Ratio of minimum to maximum transmission not present.
 The \l/2 correction factor is Not present
 
For component 2:
 wR2(int) was 0.0771 before and 0.0542 after correction.
 The Ratio of minimum to maximum transmission is 0.83.
 The \l/2 correction factor is Not present

Final HKLF 4 output contains 83943 reflections, Rint = 0.0538
 (53218 with I > 3sig(I), Rint = 0.0484)
;
_exptl_crystal_colour            'greenish blue'
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.495
_exptl_crystal_description       plank
_exptl_crystal_F_000             1004
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.960
_refine_diff_density_min         -1.127
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     759
_refine_ls_number_reflns         19328
_refine_ls_number_restraints     580
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0430
_refine_ls_R_factor_gt           0.0357
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0456P)^2^+1.8412P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0889
_refine_ls_wR_factor_ref         0.0930
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16931
_reflns_number_total             19328
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b01532_si_002.cif
_cod_data_source_block           berry534
_cod_original_cell_volume        2160.7(9)
_cod_database_code               4346444
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.867
_olex2_refinement_description
;
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. Uiso/Uaniso restraints and constraints
C25 \\sim C26 \\sim C28 \\sim C25A \\sim C26A \\sim C28A \\sim C36 \\sim C35
\\sim C37 \\sim C38 \\sim C35A \\sim C37A \\sim C38A \\sim C30 \\sim C31 \\sim
C32 \\sim C33 \\sim C34 \\sim C29A \\sim C30A \\sim C31A \\sim C32A \\sim C33A
\\sim C34A \\sim C29: within 1.7A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C14 \\sim C14A \\sim C13 \\sim C15 \\sim C12A \\sim C11A \\sim C15A \\sim C12
\\sim C10A \\sim C10 \\sim C9 \\sim C7A \\sim C7 \\sim C8A \\sim C8 \\sim C6A
\\sim C11 \\sim C6 \\sim C5A \\sim C4 \\sim C5 \\sim C4A \\sim C3 \\sim C3A:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C27A) = Uanis(C27)
Uanis(C28A) = Uanis(C28)
3. Same fragment restrains
{C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A, C11A, C12A, C14A, C15A}
as
{C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C14, C15}
{C25A, C26A, C27A, C28A, C29A, C30A, C31A, C32A, C33A, C34A, C35A, C37A, C38A}
as
{C25, C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C37, C38}
4. Others
 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(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15A)=Sof(H15D)=Sof(H15E)=
 Sof(H15F)=1-FVAR(1)
 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(C14)=Sof(H14A)=
 Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(1)
 Sof(C25A)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C27A)=Sof(H27D)=
 Sof(H27E)=Sof(H27F)=Sof(C28A)=Sof(H28C)=Sof(H28D)=Sof(C29A)=Sof(C30A)=
 Sof(H30A)=Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(C34A)=
 Sof(H34A)=Sof(C35A)=Sof(H35C)=Sof(H35D)=Sof(C37A)=Sof(H37D)=Sof(H37E)=
 Sof(H37F)=Sof(C38A)=Sof(H38D)=Sof(H38E)=Sof(H38F)=1-FVAR(2)
 Sof(C25)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27)=Sof(H27A)=Sof(H27B)=
 Sof(H27C)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(C29)=Sof(C30)=Sof(H30)=Sof(C31)=
 Sof(H31)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35A)=
 Sof(H35B)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C38)=Sof(H38A)=Sof(H38B)=
 Sof(H38C)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C12(H12A,H12B), C5A(H5AA,H5AB), C12A(H12C,H12D), C28(H28A,H28B),
 C35(H35A,H35B), C28A(H28C,H28D), C35A(H35C,H35D)
5.b Aromatic/amide H refined with riding coordinates:
 C19(H19), C20(H20), C21(H21), C7(H7), C8(H8), C9(H9), C11(H11), C7A(H7A),
 C8A(H8A), C9A(H9A), C11A(H11A), C42(H42), C43(H43), C44(H44), C30(H30),
 C31(H31), C32(H32), C34(H34), C30A(H30A), C31A(H31A), C32A(H32A), C34A(H34A)
5.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C23(H23A,H23B,H23C), 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), C40(H40A,H40B,H40C),
 C46(H46A,H46B,H46C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C37(H37A,H37B,
 H37C), C38(H38A,H38B,H38C), C26A(H26D,H26E,H26F), C27A(H27D,H27E,H27F),
 C37A(H37D,H37E,H37F), C38A(H38D,H38E,H38F)
;