Tuning the reactivity of an osmium-peroxo unit by modulating metallacycle aromaticity.
Deng, Zhihong; Zhang, Hong; Luo, Ming; Xia, Haiping; Chemical communications (Cambridge, England) 62 (2026) 5914–5918; doi:10.1039/d5cc07078c

data_7135413
_publ_section_title
;
 Tuning the reactivity of an osmium-peroxo unit by modulating metallacycle
 aromaticity.
;
_journal_issue                   21
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              5914
_journal_page_last               5918
_journal_paper_doi               10.1039/d5cc07078c
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C63 H51 Cl0.25 O4.5 Os P3, 3(C H2 Cl2)'
_chemical_formula_sum            'C66 H57 Cl6.25 O4.5 Os P3'
_chemical_formula_weight         1426.79
_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     iterative
_audit_creation_date             2025-12-12
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-12-12 deposited with the CCDC.	2026-02-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.239(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.0692(3)
_cell_length_b                   23.4824(6)
_cell_length_c                   20.1169(5)
_cell_measurement_reflns_used    6221
_cell_measurement_temperature    172.95(10)
_cell_measurement_theta_max      28.7050
_cell_measurement_theta_min      2.3320
_cell_volume                     6137.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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_environment      N~2~
_diffrn_ambient_temperature      172.95(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1903
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -73.00   0.00   1.00    5.00    --  -23.01   0.00  30.00   73
  2  \w    -11.00  16.00   1.00    5.00    --  -23.01  19.00 -90.00   27
  3  \w   -105.00 -42.00   1.00    5.00    --  -23.01 178.00 -90.00   63
  4  \w    -80.00 -21.00   1.00    5.00    --  -23.01  19.00 -90.00   59
  5  \w     61.00 101.00   1.00    5.00    --   24.26 178.00  30.00   40
  6  \w     61.00  89.00   1.00    5.00    --   24.26 178.00-150.00   28
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0128197000
_diffrn_orient_matrix_UB_12      0.0290615000
_diffrn_orient_matrix_UB_13      -0.0040295000
_diffrn_orient_matrix_UB_21      0.0448534000
_diffrn_orient_matrix_UB_22      -0.0035876000
_diffrn_orient_matrix_UB_23      0.0228180000
_diffrn_orient_matrix_UB_31      0.0283627000
_diffrn_orient_matrix_UB_32      -0.0074463000
_diffrn_orient_matrix_UB_33      -0.0268420000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0354
_diffrn_reflns_av_unetI/netI     0.0472
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            26259
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         2.214
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.477
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75132
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic blackish black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   blackish
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.544
_exptl_crystal_description       block
_exptl_crystal_F_000             2865
_exptl_crystal_size_max          0.6
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.4
_refine_diff_density_max         2.002
_refine_diff_density_min         -1.633
_refine_diff_density_rms         0.123
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.172
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     758
_refine_ls_number_reflns         10818
_refine_ls_number_restraints     52
_refine_ls_restrained_S_all      1.185
_refine_ls_R_factor_all          0.0655
_refine_ls_R_factor_gt           0.0571
_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^)+(0.0159P)^2^+48.5099P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1163
_refine_ls_wR_factor_ref         0.1199
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9625
_reflns_number_total             10818
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cc07078c2.cif
_cod_data_source_block           dzh160331-1
_cod_depositor_comments
'Adding full bibliography for 7135412--7135413.cif.'
_cod_original_cell_volume        6137.3(3)
_cod_original_formula_sum        'C66 H57 Cl6.25 O4.50 Os P3'
_cod_database_code               7135413
_shelx_shelxl_version_number     2019/3
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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
 Cl2A-C1A = Cl2A-C1B = Cl3-C1B = Cl-C1A
 1.77 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1B \\sim Cl2A \\sim C1A \\sim Cl \\sim Cl3: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
4. Others
 Fixed Sof: O2(0.75) Cl(0.25) C1A(0.25) H1AA(0.25) H1AB(0.25) O1(0.75)
 Cl1(0.25) Cl3(0.75) C1B(0.75) H1BA(0.75) H1BB(0.75)
5.a Secondary CH2 refined with riding coordinates:
 C2AA(H2AA,H2AB), C0AA(H0AA,H0AB), C1A(H1AA,H1AB), C1B(H1BA,H1BB)
5.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C5(H5), C12(H12), C3(H3), C17(H17), C10(H10), C27(H27), C25(H25),
 C34(H34), C24(H24), C46(H46), C15(H15), C21(H21), C47(H47), C50(H50), C26(H26),
  C13(H13), C29(H29), C44(H44), C14(H14), C30(H30), C58(H58), C56(H56),
 C20(H20), C19(H19), C23(H23), C18(H18), C54(H54), C38(H38), C40(H40), C35(H35),
  C33(H33), C48(H48), C53(H53), C62(H62), C52(H52), C49(H49), C59(H59),
 C31(H31), C36(H36), C55(H55), C42(H42), C32(H32), C41(H41), C43(H43), C37(H37),
  C61(H61), C60(H60)
5.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C)
;
_shelx_res_checksum              4842
_shelx_hkl_checksum              41983
_olex2_date_sample_data_collection 2016-03-31
_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 1.313
_oxdiff_exptl_absorpt_empirical_full_min 0.796