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_1576405
_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
'C32 H46 Cl3 N6 Rh2, 1.761(C2 H3 N), C F3 O3 S, 0.239(C4 H10 O)'
_chemical_formula_sum            'C37.5 H53.74 Cl3 F3 N7.75 O3.25 Rh2 S'
_chemical_formula_weight         1066.32
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_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                 98.880(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.9664(4)
_cell_length_b                   15.6304(3)
_cell_length_c                   16.1234(3)
_cell_measurement_reflns_used    21824
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      30.8820
_cell_measurement_theta_min      2.0400
_cell_volume                     4473.53(16)
_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_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     -5.00  67.00   0.50    0.40    --    5.96  37.00  30.00  144
  2  \w     29.00  68.00   0.50    0.40    --   -4.17  53.00 -71.00   78
  3  \w    -14.00  28.00   0.50    0.40    --   -4.17 -99.00-150.00   84
  4  \w    -17.00  38.00   0.50    0.40    --    5.96 -99.00 -90.00  110
  5  \w    -75.00 -37.00   0.50    0.40    --   -4.17 -53.00 144.00   76
  6  \w    -14.00  11.00   0.50    0.40    --   -4.17 -99.00 150.00   50
;
_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  0.0399
_diffrn_reflns_av_unetI/netI     0.0332
_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       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            37338
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.998
_diffrn_reflns_theta_min         1.736
_exptl_absorpt_coefficient_mu    1.021
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33557
_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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.583
_exptl_crystal_description       block
_exptl_crystal_F_000             2172
_exptl_crystal_size_max          0.581
_exptl_crystal_size_mid          0.333
_exptl_crystal_size_min          0.24
_refine_diff_density_max         1.309
_refine_diff_density_min         -0.921
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.274
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     674
_refine_ls_number_reflns         8796
_refine_ls_number_restraints     143
_refine_ls_restrained_S_all      1.267
_refine_ls_R_factor_all          0.0555
_refine_ls_R_factor_gt           0.0508
_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^)+28.4788P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1198
_refine_ls_wR_factor_ref         0.1212
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8039
_reflns_number_total             8796
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07037f2.cif
_cod_data_source_block           088-01-109-3ym
_cod_original_formula_sum        'C37.50 H53.74 Cl3 F3 N7.75 O3.25 Rh2 S'
_cod_database_code               1576405
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.792
_shelx_estimated_absorpt_t_min   0.588
_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. Restrained distances
 C40-O41
 1.41 with sigma of 0.02
 O41-C42
 1.41 with sigma of 0.02
 C39-C40
 1.54 with sigma of 0.02
 C42-C43
 1.54 with sigma of 0.02
 C18-C16 = C19-C16 = C17-C16
 1.54 with sigma of 0.02
 C18A-C16A = C19A-C16A = C17A-C16A
 1.54 with sigma of 0.02
 F2A-C37A \\sim F2-C37
 with sigma of 0.02
 S1-O2 \\sim S1-O3
 with sigma of 0.02
 S1-C37 \\sim S1A-C37A
 with sigma of 0.02
 F3-C37 \\sim F1A-C37A
 with sigma of 0.02
 S1A-O3A \\sim S1-O1
 with sigma of 0.02
 F3A-C37A \\sim F1-C37
 with sigma of 0.02
 S1A-O1A \\sim S1A-O2A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C43 \\sim C42 \\sim O41 \\sim C40 \\sim C39: within 1.7A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 1.7A
C19 \\sim C18: within 1.7A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 1.7A
C22 \\sim C21 \\sim C20 \\sim N4 \\sim C24 \\sim C23: within 1.7A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 1.7A
C18 \\sim C16 \\sim C19 \\sim C17: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C18A \\sim C16A \\sim C19A \\sim C17A: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(C17A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C40, C43, C42, O41, C39
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C19, C16, C18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C18, C16, C19, C17
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C18A, C16A, C19A, C17A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O2A)=Sof(O1A)=Sof(S1A)=Sof(O3A)=Sof(F3A)=Sof(C37A)=Sof(F1A)=Sof(F2A)=1-
 FVAR(1)
 Sof(S1)=Sof(O1)=Sof(O2)=Sof(F1)=Sof(F3)=Sof(F2)=Sof(C37)=Sof(O3)=FVAR(1)
 Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(O41)=Sof(C40)=Sof(H40A)=Sof(H40B)=
 Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=1-FVAR(2)
 Sof(C33)=Sof(N8)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(2)
 Fixed Sof: C18(0.25) H18A(0.25) H18B(0.25) H18C(0.25) C16(0.25) C19(0.25)
 H19A(0.25) H19B(0.25) H19C(0.25) Cl3(0.7) Cl6(0.3) C17(0.25) H17A(0.25)
 H17B(0.25) H17C(0.25) C19A(0.75) H19D(0.75) H19E(0.75) H19F(0.75) C16A(0.75)
 C18A(0.75) H18D(0.75) H18E(0.75) H18F(0.75) C17A(0.75) H17D(0.75) H17E(0.75)
 H17F(0.75)
6.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B),
 C40(H40A,H40B), C42(H42A,H42B)
6.b Me refined with riding coordinates:
 C39(H39A,H39B,H39C)
6.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C10(H10), C21(H21), C23(H23)
6.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C18(H18A,H18B,
 H18C), C31(H31A,H31B,H31C), C36(H36A,H36B,H36C), C26(H26A,H26B,H26C), C32(H32A,
 H32B,H32C), C30(H30A,H30B,H30C), C19(H19A,H19B,H19C), C34(H34A,H34B,H34C),
 C43(H43A,H43B,H43C), C17(H17A,H17B,H17C), C19A(H19D,H19E,H19F), C18A(H18D,H18E,
 H18F), C17A(H17D,H17E,H17F)
;
_shelx_res_checksum              70619
_shelx_hkl_checksum              31093
_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
;