Low-oxidation state dirhodium complex produced by four-electron reduction of dirhodium(ii) complex supported by a flexible macrocyclic ligand
Yan, Liping; Moriyama, Takumi; Akita, Yutaro; Muratsugu, Satoshi; Tada, Mizuki; Yamashita, Makoto; Morimoto, Yuma; Chemical Science  (2026) –; doi:10.1039/D5SC07037F

data_1576408
_publ_section_title
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 Low-oxidation state dirhodium complex produced by four-electron reduction
 of dirhodium(ii) complex supported by a flexible macrocyclic ligand
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_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC07037F
_journal_year                    2026
_chemical_formula_moiety         'C36 H54 N6 Rh2, C4 H10 O'
_chemical_formula_sum            'C40 H64 N6 O Rh2'
_chemical_formula_weight         850.79
_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     iterative
_audit_creation_date             2025-06-08
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-06-16 deposited with the CCDC.	2025-12-01 downloaded from the CCDC.
;
_cell_angle_alpha                107.213(3)
_cell_angle_beta                 91.691(3)
_cell_angle_gamma                110.555(4)
_cell_formula_units_Z            1
_cell_length_a                   9.7299(4)
_cell_length_b                   9.9420(4)
_cell_length_c                   11.2199(4)
_cell_measurement_reflns_used    4798
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      30.5220
_cell_measurement_theta_min      2.3190
_cell_volume                     959.88(7)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      93(2)
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.845
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     -6.00  85.00   0.50    4.49    --   15.87  73.00 -34.00  182
  2  \w     68.00  98.00   0.50    4.49    --   15.87 178.00 -30.00   60
  3  \w     57.00  98.00   0.50    4.49    --   15.87 178.00-180.00   82
  4  \w      4.00  91.00   0.50    4.49    --   15.87  57.00  90.00  174
  5  \w    -15.00  11.00   0.50    4.49    --  -14.15 -99.00-150.00   52
  6  \w    -48.00  46.00   0.50    4.49    --   15.87 -73.00-163.00  188
  7  \w    -53.00  36.00   0.50    4.49    --   15.87 -77.00 150.00  178
  8  \w    -90.00 -65.00   0.50    4.49    --  -14.15-178.00 -60.00   50
  9  \w    -92.00 -58.00   0.50    4.49    --  -14.15 178.00-180.00   68
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0356
_diffrn_reflns_av_unetI/netI     0.0519
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.845
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            12299
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.845
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.845
_diffrn_reflns_theta_min         2.261
_exptl_absorpt_coefficient_mu    0.899
_exptl_absorpt_correction_T_max  0.865
_exptl_absorpt_correction_T_min  0.763
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic blackish green'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   blackish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.472
_exptl_crystal_description       block
_exptl_crystal_F_000             444
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.048
_exptl_crystal_size_min          0.044
_refine_diff_density_max         2.479
_refine_diff_density_min         -0.933
_refine_diff_density_rms         0.136
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     278
_refine_ls_number_reflns         5097
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0615
_refine_ls_R_factor_gt           0.0466
_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^)+(0.0721P)^2^+0.6657P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1161
_refine_ls_wR_factor_ref         0.1236
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4178
_reflns_number_total             5097
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07037f2.cif
_cod_data_source_block           091-03-rh20-et2o
_cod_database_code               1576408
_shelx_shelxl_version_number     2019/3
_olex2_refinement_description
;
1. Restrained distances
 O1-C20 = C20-C19 = O1-C22 = C22-C23
 1.52 with sigma of 0.02
 O1-C19 = C20-C22 = O1-C23
 2.53 with sigma of 0.04
2. Others
 Fixed Sof: O1(0.5) C20(0.5) H20A(0.5) H20B(0.5) C19(0.5) H19A(0.5) H19B(0.5)
 H19C(0.5) C22(0.5) H22A(0.5) H22B(0.5) C23(0.5) H23A(0.5) H23B(0.5) H23C(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B), C15(H15A,H15B), C18(H18A,H18B), C14(H14A,
 H14B), C20(H20A,H20B), C22(H22A,H22B)
3.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C4(H4)
3.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C1(H1A,H1B,H1C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C),
 C9(H9A,H9B,H9C), C19(H19A,H19B,H19C), C23(H23A,H23B,H23C)
;
_shelx_res_checksum              86518
_shelx_hkl_checksum              92060
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- B-factor correction
;