Stimulus-responsive metallocenes: a photo/thermal switch enabled by the perfluorinated Cp* ligand
Sievers, Robin; Hartmann, Nick; Riemann, Paulin S.; Streit, Tim-Niclas; Malischewski, Moritz; Chemical Science 16 (2025) 11949–11953; doi:10.1039/D5SC02784E

data_1574731
_publ_section_title
;
 Stimulus-responsive metallocenes: a photo/thermal switch enabled by the
 perfluorinated Cp* ligand
;
_journal_issue                   26
_journal_name_full               'Chemical Science'
_journal_page_first              11949
_journal_page_last               11953
_journal_paper_doi               10.1039/D5SC02784E
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C11 H14 N3 Ru, C H2 Cl2, C10 F15'
_chemical_formula_sum            'C22 H16 Cl2 F15 N3 Ru'
_chemical_formula_weight         779.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2025-04-02
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-04-03 deposited with the CCDC.	2025-05-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 116.484(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.6437(10)
_cell_length_b                   11.1515(9)
_cell_length_c                   12.2040(11)
_cell_measurement_reflns_used    9949
_cell_measurement_temperature    100.00
_cell_measurement_theta_max      25.029
_cell_measurement_theta_min      2.610
_cell_volume                     1418.3(2)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.00
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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  0.0490
_diffrn_reflns_av_unetI/netI     0.0349
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            24628
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.044
_diffrn_reflns_theta_max         25.044
_diffrn_reflns_theta_min         2.610
_exptl_absorpt_coefficient_mu    0.859
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6356
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0981 before and 0.0639 after correction.
The Ratio of minimum to maximum transmission is 0.8529.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.825
_exptl_crystal_description       block
_exptl_crystal_F_000             764
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.208
_refine_diff_density_min         -0.654
_refine_diff_density_rms         0.101
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.47(6)
_refine_ls_extinction_coef       0.0042(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/1 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.089
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     389
_refine_ls_number_reflns         5005
_refine_ls_number_restraints     16
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0500
_refine_ls_R_factor_gt           0.0415
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0381P)^2^+4.7050P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0948
_refine_ls_wR_factor_ref         0.1046
_reflns_Friedel_coverage         0.894
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                4617
_reflns_number_total             5005
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02784e2.cif
_cod_data_source_block           sad_a
_cod_depositor_comments
'Adding full bibliography for 1574729--1574731.cif.'
_cod_database_code               1574731
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.919
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.53(6)
 0.47(6)
2. 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
3. Restrained distances
 C00X-C00Y \\sim C4-C1
 with sigma of 0.02
 C00X-C015 \\sim C4-C3
 with sigma of 0.02
 C00Y-C014 \\sim C1-C0
 with sigma of 0.02
 C014-C016 \\sim C0-C2
 with sigma of 0.02
 C015-C016 \\sim C3-C2
 with sigma of 0.02
 Ru01-C00X \\sim Ru01-C4
 with sigma of 0.04
 Ru01-C00Y \\sim Ru01-C1
 with sigma of 0.04
 Ru01-C014 \\sim Ru01-C0
 with sigma of 0.04
 Ru01-C015 \\sim Ru01-C3
 with sigma of 0.04
 Ru01-C016 \\sim Ru01-C2
 with sigma of 0.04
 C00X-C014 \\sim C4-C0
 with sigma of 0.04
 C00X-C016 \\sim C4-C2
 with sigma of 0.04
 C00Y-C015 \\sim C1-C3
 with sigma of 0.04
 C00Y-C016 \\sim C1-C2
 with sigma of 0.04
 C014-C015 \\sim C0-C3
 with sigma of 0.04
4. Others
 Sof(C1)=Sof(H1)=Sof(C0)=Sof(H0)=Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C4)=
 Sof(H4)=1-FVAR(1)
 Sof(C00X)=Sof(H00X)=Sof(C00Y)=Sof(H00Y)=Sof(C014)=Sof(H014)=Sof(C015)=
 Sof(H015)=Sof(C016)=Sof(H016)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C012(H01A,H01B)
5.b Aromatic/amide H refined with riding coordinates:
 C00X(H00X), C00Y(H00Y), C014(H014), C015(H015), C016(H016), C1(H1), C0(H0),
 C2(H2), C3(H3), C4(H4)
5.c Idealised Me refined as rotating group:
 C00I(H00A,H00B,H00C), C00S(H00D,H00E,H00F), C00W(H00G,H00H,H00I)
;
_shelx_res_checksum              30369
_olex2_submission_special_instructions 'No special instructions were received'