Accessing unsymmetrical Ru(II) bipyridine complexes: a versatile synthetic mechanism for fine tuning photophysical properties.
Hallen, Lukas; Horan, Alexandra M.; Twamley, Brendan; McGarrigle, Eoghan M.; Draper, Sylvia M.; Chemical communications (Cambridge, England) 59 (2023) 330–333; doi:10.1039/d2cc04910d

data_7131027
_publ_section_title
;
 Accessing unsymmetrical Ru(II) bipyridine complexes: a versatile
 synthetic mechanism for fine tuning photophysical properties.
;
_journal_issue                   3
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              330
_journal_page_last               333
_journal_paper_doi               10.1039/d2cc04910d
_journal_volume                  59
_journal_year                    2023
_chemical_formula_moiety
'C57 H40 F3 N7 Ru, 0.327(C H2 Cl2), 2(F6 P), 0.946(C7 H8)'
_chemical_formula_sum            'C63.95 H48.22 Cl0.65 F15 N7 P2 Ru'
_chemical_formula_weight         1385.96
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-08-24
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-09-01 deposited with the CCDC.	2022-11-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.648(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.3727(8)
_cell_length_b                   23.3211(10)
_cell_length_c                   31.2846(12)
_cell_measurement_reflns_used    9414
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      62.962
_cell_measurement_theta_min      2.934
_cell_volume                     12907.7(9)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_collection       'APEX 3 (Bruker, 2017) '
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            APEX2
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'Kappa diffractometer'
_diffrn_measurement_device_type  'Bruker APEX2 Kappa Duo'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_detector       APEX2
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.1171
_diffrn_reflns_av_unetI/netI     0.0878
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            77737
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        64.203
_diffrn_reflns_theta_max         64.203
_diffrn_reflns_theta_min         2.934
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           0.6
_diffrn_source_power             0.030
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    3.459
_exptl_absorpt_correction_T_max  0.7524
_exptl_absorpt_correction_T_min  0.6032
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1008 before and 0.0806 after correction.
The Ratio of minimum to maximum transmission is 0.8017.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.426
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       rod
_exptl_crystal_F_000             5609
_exptl_crystal_size_max          0.219
_exptl_crystal_size_mid          0.034
_exptl_crystal_size_min          0.031
_refine_diff_density_max         2.108
_refine_diff_density_min         -0.687
_refine_diff_density_rms         0.130
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     937
_refine_ls_number_reflns         10736
_refine_ls_number_restraints     427
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.1326
_refine_ls_R_factor_gt           0.0901
_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^)+(0.1858P)^2^+20.4013P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2511
_refine_ls_wR_factor_ref         0.2935
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6778
_reflns_number_total             10736
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc04910d2.cif
_cod_data_source_block           ru2
_cod_depositor_comments
'Adding full bibliography for 7131026--7131027.cif.'
_cod_database_code               7131027
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.900
_shelx_estimated_absorpt_t_min   0.518
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
C73 \\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C73B
\\sim C74B \\sim C75B \\sim C76B \\sim C77B \\sim C78B \\sim C79B: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C73B \\sim C74B \\sim C75B \\sim C76B \\sim C77B \\sim C78B \\sim C79B: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Cl3 \\sim Cl4 \\sim C25: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(C80) \\sim Ueq, Uanis(Cl1) \\sim Ueq, Uanis(Cl2) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C74) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C75)
\\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C77) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C78B) \\sim Ueq, Uanis(C73B) \\sim Ueq, Uanis(C74B) \\sim Ueq,
Uanis(C79B) \\sim Ueq, Uanis(C75B) \\sim Ueq, Uanis(C76B) \\sim Ueq,
Uanis(C77B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C66) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C68)
\\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C70) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C70) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C72)
\\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C69) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl4) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(C25) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(Cl1) \\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(Cl2) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
2. Others
 1*[Sof(C73)+Sof(H73A)+Sof(H73B)+Sof(H73C)+Sof(C74)+Sof(C75)+Sof(H75)+Sof(C76)+
 Sof(H76)+Sof(C77)+Sof(H77)+Sof(C78)+Sof(H78)+Sof(C79)+Sof(H79)]+1*[Sof(C73B)+
 Sof(H73D)+Sof(H73E)+Sof(H73F)+Sof(C74B)+Sof(C75B)+Sof(H75B)+Sof(C76B)+
 Sof(H76B)+Sof(C77B)+Sof(H77B)+Sof(C78B)+Sof(H78B)+Sof(C79B)+Sof(H79B)]+1*
 [Sof(Cl1)+Sof(Cl2)+Sof(C80)+Sof(H80A)+Sof(H80B)]=0.75 with esd of 0.01
 Sof(C73B)=Sof(H73D)=Sof(H73E)=Sof(H73F)=Sof(C74B)=Sof(C75B)=Sof(H75B)=
 Sof(C76B)=Sof(H76B)=Sof(C77B)=Sof(H77B)=Sof(C78B)=Sof(H78B)=Sof(C79B)=
 Sof(H79B)=FVAR(1)
 Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=Sof(C74)=Sof(C75)=Sof(H75)=Sof(C76)=
 Sof(H76)=Sof(C77)=Sof(H77)=Sof(C78)=Sof(H78)=Sof(C79)=Sof(H79)=FVAR(2)
 Sof(Cl1)=Sof(Cl2)=Sof(C80)=Sof(H80A)=Sof(H80B)=FVAR(3)
 Fixed Sof: Cl3(0.15) Cl4(0.15) C25(0.15) H25A(0.15) H25B(0.15) C66(0.3333)
 H66A(0.3333) H66B(0.3333) H66C(0.3333) C67(0.3333) C68(0.3333) H68(0.3333)
 C69(0.3333) H69(0.3333) C70(0.3333) H70(0.3333) C71(0.3333) H71(0.3333)
 C72(0.3333) H72(0.3333)
3.a Free rotating group:
 Cl1(Cl2,C80), Cl3(Cl4,C25), C66(C67,C68,C69,C70,C71,C72), C73(C74,C75,C76,C77,
 C78,C79), C73B(C74B,C75B,C76B,C77B,C78B,C79B)
3.b Secondary CH2 refined with riding coordinates:
 C80(H80A,H80B), C25(H25A,H25B)
3.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C11(H11), C14(H14),
 C15(H15), C16(H16), C17(H17), C20(H20), C21(H21), C22(H22), C23(H23), C28(H28),
  C29(H29), C31(H31), C32(H32), C34(H34), C37(H37), C38(H38), C41(H41),
 C43(H43), C44(H44), C48(H48), C49(H49), C51(H51), C52(H52), C55(H55), C56(H56),
  C57(H57), C58(H58), C59(H59), C61(H61), C62(H62), C63(H63), C64(H64),
 C65(H65), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72), C75(H75), C76(H76),
  C77(H77), C78(H78), C79(H79), C75B(H75B), C76B(H76B), C77B(H77B), C78B(H78B),
 C79B(H79B)
3.d Idealised Me refined as rotating group:
 C66(H66A,H66B,H66C), C73(H73A,H73B,H73C), C73B(H73D,H73E,H73F)
;
_shelx_res_checksum              40227
_shelx_hkl_checksum              41340
_olex2_exptl_crystal_mounting_method 'mounted in oil on a MiTeGen micoloop'
_olex2_submission_original_sample_id LH535Ru
_olex2_submission_special_instructions 'No special instructions were received'