Insights into the different mechanistic stages of light-induced hydrogen evolution of a 5,5′-bisphenanthroline linked RuPt complex
Lämmle, Martin; Pilz, T. David; Kutta, Roger Jan; Müßler, Marius; Mengele, Alexander K.; Görls, Helmar; Heinemann, Frank W.; Rau, Sven; Dalton Transactions  (2022) –; doi:10.1039/D2DT01727J

data_7711312
_publ_section_title
;
 Insights into the different mechanistic stages of light-induced hydrogen
 evolution of a 5,5&#x2032;-bisphenanthroline linked RuPt complex
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT01727J
_journal_year                    2022
_chemical_formula_moiety         'C60 H62 N8 Ru, 2(F6 P), 2(C H4 O)'
_chemical_formula_sum            'C62 H70 F12 N8 O2 P2 Ru'
_chemical_formula_weight         1350.27
_chemical_properties_physical    Air-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-04-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-03-25 deposited with the CCDC.	2022-09-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.089(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.7888(14)
_cell_length_b                   12.5327(9)
_cell_length_c                   18.8750(18)
_cell_measurement_reflns_used    322
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      20.00
_cell_measurement_theta_min      6.00
_cell_volume                     6217.0(8)
_computing_cell_refinement       'EVALCCD (Duisenberg, 2003)'
_computing_data_collection       'COLLECT (Bruker-Nonius, 2002)'
_computing_data_reduction        'EVALCCD (Duisenberg, 2003)'
_computing_molecular_graphics    'SHELXTL 6.12 (Bruker AXS, 2002)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXTL 6.12 (Bruker AXS, 2002)'
_diffrn_ambient_temperature      150.15
_diffrn_detector_area_resol_mean 9
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker-Nonius KappaCCD'
_diffrn_measurement_method
;
 \f- and \w-rotations with 2.00 \% and 100 sec per frame
;
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0717
_diffrn_reflns_av_unetI/netI     0.0482
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            89373
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.103
_diffrn_reflns_theta_min         3.100
_exptl_absorpt_coefficient_mu    0.390
_exptl_absorpt_correction_T_max  0.980
_exptl_absorpt_correction_T_min  0.822
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS, Bruker-AXS, 2002'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.443
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2784
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: water, methanol'
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.420
_refine_diff_density_min         -0.288
_refine_diff_density_rms         0.057
_refine_ls_abs_structure_details
;
 Flack x determined using 5197 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.008(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     897
_refine_ls_number_reflns         13613
_refine_ls_number_restraints     323
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0473
_refine_ls_R_factor_gt           0.0346
_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^)+(0.0421P)^2^+1.9181P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0732
_refine_ls_wR_factor_ref         0.0781
_reflns_Friedel_coverage         0.991
_reflns_Friedel_fraction_full    0.989
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                11804
_reflns_number_total             13613
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt01727j2.cif
_cod_data_source_block           dp0901
_cod_database_code               7711312
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.916
_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, All C(H,H,H,H,H,H) groups, All O(H) groups
2. Restrained distances
 C100-O100 \\sim C200-O200 \\sim C200-O201
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C54 \\sim C55 \\sim C56 \\sim C54A \\sim C55A \\sim C56A: within 2A with sigma
of 0.003 and sigma for terminal atoms of 0.006
F11 \\sim F12 \\sim F13 \\sim F14 \\sim F15 \\sim F16: within 2A with sigma of
0.003 and sigma for terminal atoms of 0.006
F21 \\sim F22 \\sim F23 \\sim F24 \\sim F25 \\sim F26 \\sim F21A \\sim F22A
\\sim F23A \\sim F24A \\sim F25A \\sim F26A: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01
C200 \\sim O200 \\sim O201: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(F11) \\sim Ueq, Uanis(F12) \\sim Ueq, Uanis(F13) \\sim Ueq, Uanis(F14)
\\sim Ueq, Uanis(F15) \\sim Ueq, Uanis(F16) \\sim Ueq: with sigma of 0.003 and
sigma for terminal atoms of 0.006
Uanis(F21) \\sim Ueq, Uanis(F22) \\sim Ueq, Uanis(F23) \\sim Ueq, Uanis(F24)
\\sim Ueq, Uanis(F25) \\sim Ueq, Uanis(F26) \\sim Ueq, Uanis(F21A) \\sim Ueq,
Uanis(F22A) \\sim Ueq, Uanis(F23A) \\sim Ueq, Uanis(F24A) \\sim Ueq,
Uanis(F25A) \\sim Ueq, Uanis(F26A) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C54) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C54A)
\\sim Ueq, Uanis(C55A) \\sim Ueq, Uanis(C56A) \\sim Ueq: with sigma of 0.003
and sigma for terminal atoms of 0.006
4. Same fragment restrains
{C58, C59, C60} sigma for 1-2: 0.02, 1-3: 0.04
as
{C54, C55, C56}
{C58, C59, C60} sigma for 1-2: 0.02, 1-3: 0.04
as
{C54A, C55A, C56A}
{F11, F12, F13, F14, F15, F16} sigma for 1-2: 0.02, 1-3: 0.04
as
{F21, F22, F23, F24, F25, F26}
{F11, F12, F13, F14, F15, F16} sigma for 1-2: 0.02, 1-3: 0.04
as
{F21A, F22A, F23A, F24A, F25A, F26A}
5. Others
 Sof(F21A)=Sof(F22A)=Sof(F23A)=Sof(F24A)=Sof(F25A)=Sof(F26A)=1-FVAR(1)
 Sof(F21)=Sof(F22)=Sof(F23)=Sof(F24)=Sof(F25)=Sof(F26)=FVAR(1)
 Sof(C54A)=Sof(H54D)=Sof(H54E)=Sof(H54F)=Sof(C55A)=Sof(H55D)=Sof(H55E)=
 Sof(H55F)=Sof(C56A)=Sof(H56D)=Sof(H56E)=Sof(H56F)=1-FVAR(2)
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=
 Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=FVAR(2)
 Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(O201)=Sof(H201)=1-FVAR(3)
 Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(O200)=Sof(H200)=FVAR(3)
6.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C13(H13), C15(H15),
 C16(H16), C17(H17), C20(H20), C21(H21), C22(H22), C25(H25), C26(H26), C28(H28),
  C31(H31), C33(H33), C34(H34), C43(H43), C44(H44), C46(H46), C49(H49),
 C51(H51), C52(H52)
6.b Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C40(H40A,H40B,
 H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C54(H54A,H54B,H54C), C55(H55A,
 H55B,H55C), C56(H56A,H56B,H56C), C54A(H54D,H54E,H54F), C55A(H55D,H55E,H55F),
 C56A(H56D,H56E,H56F), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,
 H60C), C100(H10A,H10B,H10C), C200(H20A,H20B,H20C), C200(H20D,H20E,H20F)
6.c Idealised tetrahedral OH refined as rotating group:
 O100(H100), O200(H200), O201(H201)
;
_shelx_res_checksum              25699
_shelx_hkl_checksum              62759
_olex2_submission_special_instructions 'No special instructions were received'