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_1576406
_publ_section_title
;
 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         'C40 H58 N10 Rh2, 4(C F3 O3 S), 2(C2 H3 N)'
_chemical_formula_sum            'C48 H64 F12 N12 O12 Rh2 S4'
_chemical_formula_weight         1563.17
_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     dual
_audit_creation_date             2025-11-21
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-11-21 deposited with the CCDC.	2025-12-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.188(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.5880(3)
_cell_length_b                   20.6879(7)
_cell_length_c                   27.0490(8)
_cell_measurement_reflns_used    24515
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      30.8760
_cell_measurement_theta_min      2.0410
_cell_volume                     6338.3(3)
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      93(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.756
_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     -1.00  25.22   0.38    4.26    --    5.96  37.00   0.00   69
  2  \w     50.00  76.22   0.38    4.26    --    5.96  37.00   0.00   69
  3  \w    -16.00  20.10   0.38    4.26    --   -4.17 -99.00 150.00   95
  4  \w    -68.00 -34.94   0.38    4.26    --    5.96 -24.00-161.00   87
  5  \w    -32.00  17.02   0.38    4.26    --    5.96 -24.00-161.00  129
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0096051000
_diffrn_orient_matrix_UB_12      0.0026064000
_diffrn_orient_matrix_UB_13      -0.0267140000
_diffrn_orient_matrix_UB_21      -0.0204014000
_diffrn_orient_matrix_UB_22      -0.0324046000
_diffrn_orient_matrix_UB_23      -0.0024380000
_diffrn_orient_matrix_UB_31      -0.0584109000
_diffrn_orient_matrix_UB_32      0.0108806000
_diffrn_orient_matrix_UB_33      -0.0008350000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0310
_diffrn_reflns_av_unetI/netI     0.0423
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.756
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            37817
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.756
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.737
_diffrn_reflns_theta_min         1.800
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Mova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.754
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.98430
_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            'metallic orangish red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.638
_exptl_crystal_description       block
_exptl_crystal_F_000             3176
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.35
_exptl_crystal_size_min          0.26
_refine_diff_density_max         1.398
_refine_diff_density_min         -1.359
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.101
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     919
_refine_ls_number_reflns         14926
_refine_ls_number_restraints     148
_refine_ls_restrained_S_all      1.129
_refine_ls_R_factor_all          0.0721
_refine_ls_R_factor_gt           0.0566
_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^)+(0.0263P)^2^+36.2879P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1229
_refine_ls_wR_factor_ref         0.1286
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12117
_reflns_number_total             14926
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07037f2.cif
_cod_data_source_block           088-02-complex2-0220
_cod_database_code               1576406
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         CNHRhOSF
_shelx_estimated_absorpt_t_max   0.828
_shelx_estimated_absorpt_t_min   0.743
_diffrn_oxdiff_ac3_digest_frames
;
01977ce6d7d1f228754fa6d59637e8b763000293cea
;
_diffrn_oxdiff_ac3_digest_hkl    41f8eeb5af1b51bc76d0b8116cc6f7a11464d3
_olex2_refinement_description
;
1. Restrained distances
 O3B-S1B = O2B-S1B = O1B-S1B
 1.44 with sigma of 0.01
 C1B-S1B
 1.83 with sigma of 0.01
 C1B-F3B = C1B-F2B = C1B-F1B
 1.34 with sigma of 0.01
 O3A-S1A = O2A-S1A = C1A-S1A
 1.44 with sigma of 0.01
 C1A-F3A = C1A-F2A = C1A-F1A
 1.34 with sigma of 0.01
 N12-C42
 1.14 with sigma of 0.02
 C41-C42
 1.47 with sigma of 0.02
 C22-C23 = C22-C24 = C22-C25
 1.54 with sigma of 0.01
 C22-C23A = C22-C24A = C22-C25A
 1.54 with sigma of 0.01
 O3B-O2B = O3B-O1B = O2B-O1B
 2.43 with sigma of 0.04
 O3A-O2A = O3A-O1A = O2A-O1A
 2.43 with sigma of 0.04
 F3B-F2B = F2B-F1B = F3B-F1B
 2.14 with sigma of 0.04
 F3A-F2A = F2A-F1A = F3A-F1A
 2.14 with sigma of 0.04
 F3B-S1B = F2B-S1B = F1B-S1B
 2.63 with sigma of 0.04
 F3A-S1A = F2A-S1A = F1A-S1A
 2.63 with sigma of 0.04
 C1B-O3B = C1B-O2B = C1B-O1B
 2.54 with sigma of 0.02
 C1A-O3A = C1A-O2A = C1A-O1A
 2.54 with sigma of 0.02
 O3A-O2A = O2A-C1A = C1A-O3A
 2.43 with sigma of 0.04
 N12-C42 \\sim N12A-C42A
 with sigma of 0.02
 C42-C41 \\sim C42A-C41A
 with sigma of 0.02
 N12-C41 \\sim N12A-C41A
 with sigma of 0.04
2. Uiso/Uaniso restraints and constraints
S1B \\sim O2B \\sim O1B \\sim O3B \\sim F3B \\sim F1B \\sim F2B \\sim C1B:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
N12 \\sim C42 \\sim C41: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
S1A \\sim O1A \\sim O2A \\sim O3A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C1A \\sim F1A \\sim F2A \\sim F3A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
3. Rigid body (RIGU) restrains
 S1B, O2B, O1B, O3B, F3B, F1B, F2B, C1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N12, C42, C41
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 S1A, O1A, O2A, O3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, F1A, F2A, F3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C23A)=Sof(H23D)=Sof(H23E)=Sof(H23F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=
 Sof(H24F)=Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=1-FVAR(1)
 Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(1)
 Sof(N12A)=Sof(C42A)=Sof(C41A)=Sof(H41D)=Sof(H41E)=Sof(H41F)=1-FVAR(2)
 Sof(N12)=Sof(C42)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=FVAR(2)
 Fixed Sof: S1B(0.45) O2B(0.45) O1B(0.45) O3B(0.45) F3B(0.45) F1B(0.45)
 F2B(0.45) C1B(0.45) S1A(0.55) O3A(0.55) O2A(0.55) C1A(0.55) F3A(0.55)
 F2A(0.55) F1A(0.55) O1A(0.55)
5.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C35(H35A,H35B), C31(H31A,H31B), C30(H30A,H30B), C16(H16A,
 H16B), C32(H32A,H32B)
5.b Aromatic/amide H refined with riding coordinates:
 C20(H20), C12(H12), C26(H26), C10(H10)
5.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C29(H29A,H29B,H29C), C13(H13A,H13B,H13C), C01K(H01A,H01B,
 H01C), C01R(H01D,H01E,H01F), C11(H11A,H11B,H11C), C01V(H01G,H01H,H01I),
 C020(H02A,H02B,H02C), C8(H8A,H8B,H8C), C34(H34A,H34B,H34C), C25(H25A,H25B,
 H25C), C7(H7A,H7B,H7C), C9(H9A,H9B,H9C), C24(H24A,H24B,H24C), C23(H23A,H23B,
 H23C), C23A(H23D,H23E,H23F), C24A(H24D,H24E,H24F), C25A(H25D,H25E,H25F),
 C41(H41A,H41B,H41C), C41A(H41D,H41E,H41F)
;
_shelx_res_checksum              12587
_shelx_hkl_checksum              34033
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.069
_oxdiff_exptl_absorpt_empirical_full_min 0.936