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_1576407
_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
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC07037F
_journal_year                    2026
_chemical_formula_moiety         'C32 H48 N6 Rh2, C4 H8 O'
_chemical_formula_sum            'C36 H56 N6 O Rh2'
_chemical_formula_weight         794.68
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-11-12
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-11-12 deposited with the CCDC.	2025-12-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.308(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.9151(3)
_cell_length_b                   10.8332(2)
_cell_length_c                   34.3806(7)
_cell_measurement_reflns_used    30604
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      31.0690
_cell_measurement_theta_min      1.9530
_cell_volume                     7002.3(2)
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      93(2)
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -38.00  10.00   0.50    2.00    --   -4.17 -57.00  60.00   96
  2  \w    -19.00  13.00   0.50    2.00    --   -4.17 -99.00  30.00   64
  3  \w    -17.00  34.00   0.50    2.00    --    5.96 -99.00   0.00  102
  4  \w    -19.00  29.00   0.50    2.00    --   -4.17 -99.00 -90.00   96
  5  \w    -48.00 -22.00   0.50    2.00    --    5.96 -37.00  90.00   52
  6  \w    -35.00  27.00   0.50    2.00    --    5.96 -92.00 144.00  124
  7  \w    -12.00  13.00   0.50    2.00    --    5.96  92.00-103.00   50
  8  \w     17.00  42.00   0.50    2.00    --    5.96  92.00-103.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku, XtaLAB Synergy-MoNG01'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0609
_diffrn_reflns_av_unetI/netI     0.0389
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            62381
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         1.972
_exptl_absorpt_coefficient_mu    0.980
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.03145
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.508
_exptl_crystal_description       needle
_exptl_crystal_F_000             3296
_exptl_crystal_size_max          0.592
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.07
_refine_diff_density_max         4.346
_refine_diff_density_min         -3.167
_refine_diff_density_rms         0.157
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.134
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     877
_refine_ls_number_reflns         12365
_refine_ls_number_restraints     102
_refine_ls_restrained_S_all      1.135
_refine_ls_R_factor_all          0.0820
_refine_ls_R_factor_gt           0.0741
_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^)+(0.0195P)^2^+113.6590P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1564
_refine_ls_wR_factor_ref         0.1602
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11022
_reflns_number_total             12365
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07037f2.cif
_cod_data_source_block           088-01-135-03
_cod_database_code               1576407
_shelx_shelxl_version_number     2019/3
_olex2_refinement_description
;
1. Restrained distances
 C67-C66
 1.49 with sigma of 0.01
 C65-O1
 1.42 with sigma of 0.01
 C68-O1
 1.42 with sigma of 0.01
 C66-C65
 1.48 with sigma of 0.01
 C67-C68
 1.49 with sigma of 0.01
 C23-C22
 1.54 with sigma of 0.01
 C51A-C50
 1.52 with sigma of 0.01
 C43-C40
 1.52 with sigma of 0.01
 C50-C53A
 1.54 with sigma of 0.02
 C22-C77 = C22-C76 = C22-C24
 1.52 with sigma of 0.02
 C50-C51A = C50-C51B = C50-C52A = C50-C52B = C50-C53A = C50-C53B
 1.54 with sigma of 0.02
 C51A-C52A = C52A-C53A = C51A-C53A = C53B-C52B = C53B-C51B = C51B-C52B
 2.5 with sigma of 0.04
 C50-C51A \\sim C50-C51B
 with sigma of 0.02
 C50-C53A \\sim C50-C53B
 with sigma of 0.02
 C50-C52A \\sim C50-C52B
 with sigma of 0.02
2. Rigid bond restraints
 C50, C52A, C51A, C53A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C52A \\sim C51A \\sim C53A \\sim C50: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
C48 \\sim N8: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C49 \\sim N8: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
C50 \\sim C51A \\sim C52A \\sim C53A: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C22 \\sim C24 \\sim C25: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C50 \\sim C51B \\sim C52B \\sim C53B: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 C49, N8, C48
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C51A(0.8) H51A(0.8) H51B(0.8) H51C(0.8) C23(0.75) H23A(0.75)
 H23B(0.75) H23C(0.75) C24(0.75) H24A(0.75) H24B(0.75) H24C(0.75) C25(0.75)
 H25A(0.75) H25B(0.75) H25C(0.75) C78(0.25) H78A(0.25) H78B(0.25) H78C(0.25)
 C77(0.25) H77A(0.25) H77B(0.25) H77C(0.25) C76(0.25) H76A(0.25) H76B(0.25)
 H76C(0.25) C53A(0.8) H53A(0.8) H53B(0.8) H53C(0.8) C52A(0.8) H52A(0.8)
 H52B(0.8) H52C(0.8) C53B(0.2) H53D(0.2) H53E(0.2) H53F(0.2) C52B(0.2)
 H52D(0.2) H52E(0.2) H52F(0.2) C51B(0.2) H51D(0.2) H51E(0.2) H51F(0.2)
6.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B), C62(H62A,H62B), C63(H63A,H63B), C16(H16A,
 H16B), C48(H48A,H48B), C46(H46A,H46B), C32(H32A,H32B), C30(H30A,H30B),
 C47(H47A,H47B), C64(H64A,H64B), C31(H31A,H31B), C73(H73A,H73B), C70(H70A,H70B),
  C65(H65A,H65B), C72(H72A,H72B), C68(H68A,H68B), C71(H71A,H71B), C67(H67A,
 H67B), C66(H66A,H66B)
6.b Aromatic/amide H refined with riding coordinates:
 C6(H6), C52(H52), C58(H58), C12(H12), C20(H20), C26(H26), C38(H38), C44(H44)
6.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C13(H13A,H13B,H13C), C54(H54A,H54B,H54C), C61(H61A,H61B,
 H61C), C9(H9A,H9B,H9C), C29(H29A,H29B,H29C), C18(H18A,H18B,H18C), C45(H45A,
 H45B,H45C), C11(H11A,H11B,H11C), C37(H37A,H37B,H37C), C10(H10A,H10B,H10C),
 C43(H43A,H43B,H43C), C51A(H51A,H51B,H51C), C42(H42A,H42B,H42C), C41(H41A,H41B,
 H41C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C78(H78A,
 H78B,H78C), C77(H77A,H77B,H77C), C76(H76A,H76B,H76C), C53A(H53A,H53B,H53C),
 C52A(H52A,H52B,H52C), C53B(H53D,H53E,H53F), C52B(H52D,H52E,H52F), C51B(H51D,
 H51E,H51F)
;
_shelx_res_checksum              82408
_shelx_hkl_checksum              79889
_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
;