Molecular precursor synthesis of the Rh<sub>2</sub>O<sub>3</sub>/Fe<sub>2</sub>O<sub>3</sub> spherical architecture for enhanced acidic HER activity and durability.
Zulqarnain, Muhammad; Wei, Zheng; Hollo, Marcell; Dunn, Kathleen A.; Dikarev, Evgeny V.; Chemical science 16 (2025) 18695–18704; doi:10.1039/d5sc04912a

data_1575796
_publ_section_title
;
 Molecular precursor synthesis of the
 Rh<sub>2</sub>O<sub>3</sub>/Fe<sub>2</sub>O<sub>3</sub> spherical
 architecture for enhanced acidic HER activity and durability.
;
_journal_issue                   40
_journal_name_full               'Chemical science'
_journal_page_first              18695
_journal_page_last               18704
_journal_paper_doi               10.1039/d5sc04912a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C15 H21 O6 Rh'
_chemical_formula_sum            'C15 H21 O6 Rh'
_chemical_formula_weight         400.23
_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     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-05-30
_audit_creation_method
;
Olex2 1.5-ac7-014
(compiled 2025.02.27 svn.r6f4c0eaf for Rigaku Oxford Diffraction, GUI svn.r7171)
;
_audit_update_record
;
2025-06-30 deposited with the CCDC.	2025-09-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.865(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.6520(3)
_cell_length_b                   7.41605(15)
_cell_length_c                   16.2743(4)
_cell_measurement_reflns_used    19775
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      32.3210
_cell_measurement_theta_min      2.5320
_cell_volume                     1627.99(6)
_computing_cell_refinement       'CrysAlisPro 1.171.44.112a (Rigaku OD, 2025)'
_computing_data_collection       'CrysAlisPro 1.171.44.112a (Rigaku OD, 2025)'
_computing_data_reduction        'CrysAlisPro 1.171.44.112a (Rigaku OD, 2025)'
_computing_molecular_graphics    'Olex2 1.5-ac7-014 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac7-014 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.858
_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  87.00   0.50   25.00    --   11.26  34.00 120.00  184
  2  \w    -64.00  18.00   0.50   25.00    --   11.26 -34.00 -36.00  164
  3  \w    -23.00  26.00   0.50   25.00    --   -9.86 -99.00-150.00   98
  4  \w    -65.00   5.00   0.50   25.00    --   11.26 -19.00 -30.00  140
  5  \w    -23.00  47.00   0.50   25.00    --   11.26 -99.00 -60.00  140
  6  \w    -23.00  26.00   0.50   25.00    --   -9.86 -99.00 -60.00   98
  7  \w    -65.00 -40.00   0.50   25.00    --   11.26 -19.00  30.00   50
  8  \w    -23.00  47.00   0.50   25.00    --   11.26 -99.00 150.00  140
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0494204000
_diffrn_orient_matrix_UB_12      0.0307190000
_diffrn_orient_matrix_UB_13      -0.0114250000
_diffrn_orient_matrix_UB_21      0.0112707000
_diffrn_orient_matrix_UB_22      0.0278344000
_diffrn_orient_matrix_UB_23      -0.0391838000
_diffrn_orient_matrix_UB_31      -0.0139943000
_diffrn_orient_matrix_UB_32      -0.0861694000
_diffrn_orient_matrix_UB_33      -0.0167509000
_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  0.0215
_diffrn_reflns_av_unetI/netI     0.0172
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.858
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            26471
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.858
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.169
_diffrn_reflns_theta_min         2.533
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.074
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.97455
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.112a (Rigaku Oxford Diffraction, 2025)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.633
_exptl_crystal_description       block
_exptl_crystal_F_000             816
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.472
_refine_diff_density_min         -1.467
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     271
_refine_ls_number_reflns         4915
_refine_ls_number_restraints     203
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0258
_refine_ls_R_factor_gt           0.0214
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0225P)^2^+0.9722P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0502
_refine_ls_wR_factor_ref         0.0523
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4415
_reflns_number_total             4915
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04912a2.cif
_cod_data_source_block           Rh(acac)3
_cod_depositor_comments
'Adding full bibliography for 1575793--1575796.cif.'
_cod_original_cell_volume        1628.00(6)
_cod_original_sg_symbol_H-M      'P 21/c'
_cod_database_code               1575796
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.938
_shelx_estimated_absorpt_t_min   0.900
_diffrn_oxdiff_digest_hkl
;
43295351713104aa6bf0c43bc666f4628a7c78
;
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Rh1-O3 \\sim Rh1-O3X
 with sigma of 0.02
 Rh1-O4 \\sim Rh1-O4X
 with sigma of 0.02
 O3-C7 \\sim O3X-C7X
 with sigma of 0.02
 O4-C9 \\sim O4X-C9X
 with sigma of 0.02
 C9-C8 \\sim C9X-C8X
 with sigma of 0.02
 C9-C10 \\sim C9X-C10X
 with sigma of 0.02
 C7-C8 \\sim C7X-C8X
 with sigma of 0.02
 C7-C6 \\sim C7X-C6X
 with sigma of 0.02
 Rh1-C9 \\sim Rh1-C9X
 with sigma of 0.04
 Rh1-C7 \\sim Rh1-C7X
 with sigma of 0.04
 O3-C8 \\sim O3X-C8X
 with sigma of 0.04
 O3-C6 \\sim O3X-C6X
 with sigma of 0.04
 O4-C8 \\sim O4X-C8X
 with sigma of 0.04
 O4-C10 \\sim O4X-C10X
 with sigma of 0.04
 C9-C7 \\sim C9X-C7X
 with sigma of 0.04
 C8-C10 \\sim C8X-C10X
 with sigma of 0.04
 C8-C6 \\sim C8X-C6X
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O3 \\sim O4 \\sim C9 \\sim C7 \\sim C8 \\sim C10 \\sim C6 \\sim C6X \\sim C7X
\\sim O3X \\sim O4X \\sim C9X \\sim C8X \\sim C10X: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(C6X)=Sof(H6XA)=Sof(H6XB)=Sof(H6XC)=Sof(C7X)=Sof(O3X)=Sof(O4X)=Sof(C9X)=
 Sof(C8X)=Sof(H8X)=Sof(C10X)=Sof(H10D)=Sof(H10E)=Sof(H10F)=1-FVAR(1)
 Sof(O3)=Sof(O4)=Sof(C9)=Sof(C7)=Sof(C8)=Sof(H8)=Sof(C10)=Sof(H10A)=Sof(H10B)=
 Sof(H10C)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C13(H13), C3(H3), C8(H8), C8X(H8X)
5.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C11(H11A,H11B,H11C), C15(H15A,H15B,H15C), C5(H5A,H5B,H5C),
 C10(H10A,H10B,H10C), C6(H6A,H6B,H6C), C6X(H6XA,H6XB,H6XC), C10X(H10D,H10E,H10F)
;
_shelx_res_checksum              13914
_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 1.123
_oxdiff_exptl_absorpt_empirical_full_min 0.923