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_4346442
_publ_section_title
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 Axial Ligand Coordination to the C-H Amination Catalyst Rh2(esp)2: A
 Structural and Spectroscopic Study.
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_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         'C42 H50 N2 O8 Rh2, C H2 Cl2'
_chemical_formula_sum            'C43 H52 Cl2 N2 O8 Rh2'
_chemical_formula_weight         1001.58
_chemical_name_common            'Compound 2'
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-05-16
_audit_creation_method
;
Olex2 1.2
(compiled 2014.03.20 svn.r2914 for OlexSys, GUI svn.r4816)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.4895(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.3780(7)
_cell_length_b                   10.4361(4)
_cell_length_c                   23.1475(8)
_cell_measurement_reflns_used    9844
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      30.67
_cell_measurement_theta_min      2.25
_cell_volume                     4425.9(3)
_computing_cell_refinement       'SAINT+ Ver. 8.34A (Bruker-AXS, 2014)'
_computing_data_collection       'APEX2 Ver. 2014.1-1 (Bruker-AXS, 2014)'
_computing_data_reduction        'SAINT+ Ver. 8.34A (Bruker-AXS, 2014)'
_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_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '0.5\ \w and 0.5\ \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_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  0.0275
_diffrn_reflns_av_unetI/netI     0.0138
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            62054
_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         30.549
_diffrn_reflns_theta_min         1.765
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.918
_exptl_absorpt_correction_T_max  0.9793
_exptl_absorpt_correction_T_min  0.8560
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0962 before and 0.0399 after correction.
The Ratio of minimum to maximum transmission is 0.8741.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.503
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2048
_exptl_crystal_size_max          0.227
_exptl_crystal_size_mid          0.128
_exptl_crystal_size_min          0.078
_refine_diff_density_max         0.825
_refine_diff_density_min         -0.628
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.115
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     308
_refine_ls_number_reflns         6754
_refine_ls_number_restraints     73
_refine_ls_restrained_S_all      1.123
_refine_ls_R_factor_all          0.0280
_refine_ls_R_factor_gt           0.0259
_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^)+(0.0203P)^2^+10.7294P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0612
_refine_ls_wR_factor_ref         0.0625
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6385
_reflns_number_total             6754
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ic5b01532_si_002.cif
_cod_data_source_block           berry523
_cod_database_code               4346442
_shelxl_version_number           2013-3
_shelx_estimated_absorpt_t_max   0.932
_shelx_estimated_absorpt_t_min   0.819
_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
Cl1 \\sim Cl2 \\sim C22 \\sim Cl1A \\sim Cl2A \\sim C22A \\sim Cl1B \\sim Cl2B
\\sim C22B: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Others
 1*[Sof(Cl1)+Sof(Cl2)+Sof(C22)+Sof(H22A)+Sof(H22B)]+1*[Sof(Cl1A)+Sof(Cl2A)+
 Sof(C22A)+Sof(H22C)+Sof(H22D)]+1*[Sof(Cl1B)+Sof(Cl2B)+Sof(C22B)+Sof(H22E)+
 Sof(H22F)]=0.5 with esd of 0
 Sof(Cl1)=Sof(Cl2)=Sof(C22)=Sof(H22A)=Sof(H22B)=FVAR(1)
 Sof(Cl1A)=Sof(Cl2A)=Sof(C22A)=Sof(H22C)=Sof(H22D)=FVAR(2)
 Sof(Cl1B)=Sof(Cl2B)=Sof(C22B)=Sof(H22E)=Sof(H22F)=FVAR(3)
4.a Free rotating group:
 Cl1(Cl2,C22), Cl1A(Cl2A,C22A), Cl1B(Cl2B,C22B)
4.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C12(H12A,H12B), C22(H22A,H22B), C22A(H22C,H22D), C22B(H22E,H22F)
4.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C11(H11), C17(H17), C18(H18), C19(H19), C20(H20),
 C21(H21)
4.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C)
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