Immobilising molecular Ru complexes on a protective ultrathin oxide layer of p-Si electrodes towards photoelectrochemical CO<sub>2</sub> reduction.
Laurans, Maxime; Wells, Jordann A. L.; Ott, Sascha; Dalton transactions (Cambridge, England : 2003) 50 (2021) 10482–10492; doi:10.1039/d1dt01331a

data_7707833
_publ_section_title
;
 Immobilising molecular Ru complexes on a protective ultrathin oxide layer
 of p-Si electrodes towards photoelectrochemical CO<sub>2</sub> reduction.
;
_journal_issue                   30
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10482
_journal_page_last               10492
_journal_paper_doi               10.1039/d1dt01331a
_journal_volume                  50
_journal_year                    2021
_chemical_formula_moiety         '2(C28 H24 N6 O Ru), 4(F6 P), H2 O, C4 H10 O'
_chemical_formula_sum            'C60 H60 F24 N12 O4 P4 Ru2'
_chemical_formula_weight         1795.22
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2021-02-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2021-02-01 deposited with the CCDC.	2021-07-13 downloaded from the CCDC.
;
_cell_angle_alpha                90.689(6)
_cell_angle_beta                 96.845(6)
_cell_angle_gamma                118.958(5)
_cell_formula_units_Z            2
_cell_length_a                   13.989(3)
_cell_length_b                   14.256(3)
_cell_length_c                   23.355(4)
_cell_measurement_reflns_used    9751
_cell_measurement_temperature    170
_cell_measurement_theta_max      26.49
_cell_measurement_theta_min      2.26
_cell_volume                     4033.2(14)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      170
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0676
_diffrn_reflns_av_unetI/netI     0.0362
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            210324
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.368
_diffrn_reflns_theta_min         1.638
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.558
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6943
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1009 before and 0.0699 after correction. The Ratio of minimum to maximum transmission is 0.9309. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.478
_exptl_crystal_description       block
_exptl_crystal_F_000             1800
_exptl_crystal_size_max          0.359
_exptl_crystal_size_mid          0.245
_exptl_crystal_size_min          0.098
_refine_diff_density_max         1.207
_refine_diff_density_min         -0.810
_refine_diff_density_rms         0.093
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.115
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1180
_refine_ls_number_reflns         22061
_refine_ls_number_restraints     1494
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.0769
_refine_ls_R_factor_gt           0.0609
_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^)+(0.0474P)^2^+10.6339P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1450
_refine_ls_wR_factor_ref         0.1539
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17762
_reflns_number_total             22061
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt01331a2.cif
_cod_data_source_block           so2010
_cod_depositor_comments
'Adding full bibliography for 7707833--7707834.cif.'
_cod_original_cell_volume        4033.3(13)
_cod_database_code               7707833
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.825
_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, All O(H) groups
2. Restrained distances
 O1-H1
 0.95 with sigma of 0.02
 O1S-H1SD = O1S-H1SC
 0.95 with sigma of 0.02
 H1SC-H1SD
 1.5 with sigma of 0.02
 O2-H2A
 0.95 with sigma of 0.02
 H2A-C36
 1.85 with sigma of 0.02
 F24B-F23B \\sim F24B-F21B \\sim F24B-F20B \\sim F24B-F22B \\sim F23B-F19B
\\sim F23B-F20B \\sim F23B-
 F22B \\sim F19B-F21B \\sim F19B-F20B \\sim F19B-F22B \\sim F21B-F20B \\sim
F21B-F22B
 with sigma of 0.02
 P4B-F24B \\sim P4B-F23B \\sim P4B-F20B \\sim P4B-F21B \\sim P4B-F22B \\sim
P4B-F19B
 with sigma of 0.02
 P4A-F24A \\sim P4A-F22A \\sim P4A-F23A \\sim P4A-F20A \\sim P4A-F21A \\sim
P4A-F19A
 with sigma of 0.02
 F24A-F23A \\sim F24A-F21A \\sim F24A-F22A \\sim F24A-F20A \\sim F23A-F22A
\\sim F23A-F20A \\sim F23A-
 F19A \\sim F19A-F21A \\sim F19A-F22A \\sim F19A-F20A \\sim F21A-F22A \\sim
F21A-F20A
 with sigma of 0.02
 O2-H2A \\sim O1-H1
 with sigma of 0.02
3. Restrained planarity
 P4A, F24A, F23A, F19A, F21A
 with sigma of 0.1
 P4A, F24A, F22A, F19A, F20A
 with sigma of 0.1
 P4B, F24B, F23B, F19B, F21B
 with sigma of 0.1
 P4B, F24B, F19B, F21B, F22B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
N4B \\sim C16B \\sim C17B \\sim C18B \\sim C19B \\sim C20B: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C26B \\sim C25B \\sim C24B \\sim N5A \\sim C21B \\sim C22B \\sim C23B: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C26A \\sim C25A \\sim C24A \\sim C23A \\sim C22A \\sim N5B: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
N11A \\sim C49A \\sim C50A \\sim C51A \\sim C52A \\sim C53A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
N4A \\sim C16A \\sim C18B \\sim C19A \\sim C20A \\sim C21A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
N11A \\sim N10A \\sim C48A \\sim C49A \\sim C44A \\sim C50A \\sim C45A \\sim
C47A \\sim C46A \\sim C53A \\sim C54A \\sim C52A \\sim C51A \\sim N11B \\sim
C50B \\sim C51B \\sim C52B \\sim C53B \\sim C54B \\sim N10B \\sim C44B \\sim
C46B \\sim C47B \\sim C48B \\sim C49B \\sim C45B: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
N6 \\sim C27 \\sim C28 \\sim N5A \\sim C25B \\sim C24B \\sim C23B \\sim C22B
\\sim C21B \\sim C26B \\sim N4A \\sim C21A \\sim C20A \\sim C19A \\sim C18A
\\sim C16A \\sim C17A \\sim N4B \\sim C20B \\sim C19B \\sim C18B \\sim C17B
\\sim C16B \\sim C25A \\sim C24A \\sim C23A \\sim C22A \\sim N5B \\sim C26A:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C25A) = Uanis(C16B)
Uanis(C52B) = Uanis(C47B)
Uanis(N5B) = Uanis(N5A)
5. Rigid body (RIGU) restrains
 N4B, C16B, C17B, C18B, C19B, C20B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26B, C25B, C24B, N5A, C21B, C22B, C23B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C26A, C25A, C24A, C23A, C22A, N5B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4A, C16A, C18B, C19A, C20A, C21A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N11A, C49A, C50A, C51A, C52A, C53A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N11A, N10A, C48A, C49A, C44A, C50A, C45A, C47A, C46A, C53A, C54A, C52A, C51A,
 N11B, C50B, C51B, C52B, C53B, C54B, N10B, C44B, C46B, C47B, C48B, C49B, C45B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N6, C27, C28, N5A, C25B, C24B, C23B, C22B, C21B, C26B, N4A, C21A, C20A, C19A,
 C18A, C16A, C17A, N4B, C20B, C19B, C18B, C17B, C16B, C25A, C24A, C23A, C22A,
 N5B, C26A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: N11A(0.75) N10A(0.75) C48A(0.75) C49A(0.75) C44A(0.75) H54A(0.75)
 C50A(0.75) H48A(0.75) C45A(0.75) H53A(0.75) C47A(0.75) H51A(0.75) C46A(0.75)
 H52A(0.75) C53A(0.75) C54A(0.75) H45A(0.75) H45B(0.75) H45C(0.75) C52A(0.75)
 H46A(0.75) C51A(0.75) H47A(0.75) N5A(0.5) C25B(0.5) C24B(0.5) H18B(0.5)
 C23B(0.5) H19B(0.5) C22B(0.5) H20B(0.5) C21B(0.5) C26B(0.5) H17A(0.5)
 H17B(0.5) H17C(0.5) N4A(0.5) C21A(0.5) C20A(0.5) H20A(0.5) C19A(0.5) H19A(0.5)
 C18A(0.5) H18A(0.5) C16A(0.5) P4A(0.5) F24B(0.5) F20A(0.5) F21A(0.5) F19A(0.5)
 F23A(0.5) F22A(0.5) P4B(0.5) F22B(0.5) F23B(0.5) F20B(0.5) F21B(0.5) F19B(0.5)
 F24A(0.5) C17A(0.5) H17D(0.5) H17E(0.5) H17F(0.5) N4B(0.5) C20B(0.5) C19B(0.5)
 H23B(0.5) C18B(0.5) H18(0.5) C17B(0.5) H24B(0.5) C16B(0.5) H25B(0.5) C25A(0.5)
 H25A(0.5) C24A(0.5) H24A(0.5) C23A(0.5) H23A(0.5) C22A(0.5) N5B(0.5) C26A(0.5)
 H26A(0.5) N11B(0.25) C50B(0.25) C51B(0.25) H51B(0.25) C52B(0.25) H52B(0.25)
 C53B(0.25) H53B(0.25) C54B(0.25) H54B(0.25) N10B(0.25) C44B(0.25) C46B(0.25)
 H46B(0.25) C47B(0.25) H47B(0.25) C48B(0.25) H48B(0.25) C49B(0.25) C45B(0.25)
 H45D(0.25) H45E(0.25) H45F(0.25)
7.a Secondary CH2 refined with riding coordinates:
 C3S(H3SA,H3SB), C1S(H1SA,H1SB)
7.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C1(H1A), C7(H7), C29(H29), C4(H4), C15(H15), C9(H9), C2(H2),
 C32(H32), C14(H14), C3(H3), C30(H30), C13(H13), C37(H37), C35(H35), C31(H31),
 C44A(H54A), C43(H43), C42(H42), C40(H40), C50A(H48A), C45A(H53A), C47A(H51A),
 C41(H41), C46A(H52A), C52A(H46A), C51A(H47A), C24B(H18B), C23B(H19B),
 C22B(H20B), C20A(H20A), C19A(H19A), C18A(H18A), C19B(H23B), C18B(H18),
 C17B(H24B), C16B(H25B), C25A(H25A), C24A(H24A), C23A(H23A), C26A(H26A),
 C51B(H51B), C52B(H52B), C53B(H53B), C54B(H54B), C46B(H46B), C47B(H47B),
 C48B(H48B)
7.c Fitted hexagon refined as free rotating group:
 N5A(C25B,C24B,C23B,C22B,C21B), N4A(C21A,C20A,C19A,C18A,C16A), N4B(C20B,C19B,
 C18B,C17B,C16B), C25A(C24A,C23A,C22A,N5B,C26A), N11B(C50B,C51B,C52B,C53B,C54B),
  N10B(C44B,C46B,C47B,C48B,C49B)
7.d Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C56(H56A,H56B,H56C), C54A(H45A,H45B,H45C), C4S(H4SA,H4SB,
 H4SC), C2S(H2SA,H2SB,H2SC), C26B(H17A,H17B,H17C), C17A(H17D,H17E,H17F),
 C45B(H45D,H45E,H45F)
7.e Idealised tetrahedral OH refined as rotating group:
 O2(H2A)
;
_shelx_res_checksum              54675
_shelx_fab_checksum              66479
_olex2_submission_special_instructions 'No special instructions were received'