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_7131026
_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
'C55 H40 F3 N7 Ru, 0.375(C7 H8), 2(F6 P), 0.75(C H2 Cl2)'
_chemical_formula_sum            'C58.38 H44.5 Cl1.5 F15 N7 P2 Ru'
_chemical_formula_weight         1345.19
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-06-24
_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                107.594(6)
_cell_angle_beta                 98.679(6)
_cell_angle_gamma                109.219(4)
_cell_formula_units_Z            4
_cell_length_a                   17.5338(13)
_cell_length_b                   19.1373(12)
_cell_length_c                   20.747(2)
_cell_measurement_reflns_used    3392
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      61.848
_cell_measurement_theta_min      2.640
_cell_volume                     6018.8(9)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_collection       'APEX 4 (Bruker, 2021) '
_computing_data_reduction        'SAINT V8.40B (Bruker, 2016)'
_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    '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 0.974
_diffrn_measured_fraction_theta_max 0.974
_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  0.1178
_diffrn_reflns_av_unetI/netI     0.1110
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            19160
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        63.365
_diffrn_reflns_theta_max         63.365
_diffrn_reflns_theta_min         2.640
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           0.6
_diffrn_source_power             0.029778
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           49.63
_exptl_absorpt_coefficient_mu    4.026
_exptl_absorpt_correction_T_max  0.7522
_exptl_absorpt_correction_T_min  0.5501
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.1107 before and 0.0795 after correction.
 
For component 2:
 wR2(int) was 0.1179 before and 0.0849 after correction.
 The Ratio of minimum to maximum transmission is 0.60.

Final HKLF 4 output contains 58829 reflections, Rint = 0.1076
 (17281 with I > 3sig(I), Rint = 0.0760)
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.485
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             2713
_exptl_crystal_size_max          0.227
_exptl_crystal_size_mid          0.093
_exptl_crystal_size_min          0.032
_refine_diff_density_max         4.870
_refine_diff_density_min         -1.816
_refine_diff_density_rms         0.236
_refine_ls_extinction_coef       0.0009(3)
_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   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1625
_refine_ls_number_reflns         19160
_refine_ls_number_restraints     873
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.1827
_refine_ls_R_factor_gt           0.1497
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.4150P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4500
_refine_ls_wR_factor_ref         0.4995
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13190
_reflns_number_total             19160
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc04910d2.cif
_cod_data_source_block           ru1
_cod_depositor_comments
'Adding full bibliography for 7131026--7131027.cif.'
_cod_original_formula_sum        'C58.38 H44.50 Cl1.50 F15 N7 P2 Ru'
_cod_database_code               7131026
_shelx_shelxl_version_number     2019/1
_shelx_estimated_absorpt_t_max   0.882
_shelx_estimated_absorpt_t_min   0.462
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.646(6)
 0.354(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
 F1A-C25 = F1B-C25 = F2A-C25 = F2B-C25 = F3B-C25 = F3A-C25
 1.28 with sigma of 0.01
 F1A-F2A
 2 with sigma of 0.01
 F2A-F3A
 2 with sigma of 0.01
 F3A-F1A
 2 with sigma of 0.01
 F1B-F2B
 2 with sigma of 0.01
 F2B-F3B
 2 with sigma of 0.01
 F3B-F1B
 2 with sigma of 0.01
 N50-C57B \\sim N50-C57A
 with sigma of 0.01
4. Restrained planarity
 N50, C57B, C62B, C57A, C62A
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C57B \\sim C58B \\sim C59B \\sim C60B \\sim C61B \\sim C62B \\sim C57A \\sim
C58A \\sim C59A \\sim C60A \\sim C61A \\sim C62A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
Cl3 \\sim Cl4 \\sim C126: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Cl3 \\sim Cl4 \\sim C126 \\sim Cl1 \\sim Cl2 \\sim C125: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08 within 2A
C143 \\sim C144 \\sim C145 \\sim C146 \\sim C147 \\sim C148 \\sim C149: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C143 \\sim C144 \\sim C145 \\sim C146 \\sim C147 \\sim C148 \\sim C149 \\sim
Cl9 \\sim Cl10 \\sim C129: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C130 \\sim C131 \\sim C132 \\sim C133 \\sim C134 \\sim C135 \\sim C136 \\sim
Cl5 \\sim Cl6 \\sim C127: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C96 \\sim C137 \\sim C138 \\sim C139 \\sim C140 \\sim C141 \\sim C142 \\sim Cl7
\\sim Cl8 \\sim C128: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
C143 \\sim C144 \\sim C145 \\sim C146 \\sim C147 \\sim C148 \\sim C149 \\sim
Cl10 \\sim Cl9 \\sim C129: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Cl4 \\sim Cl3 \\sim C126 \\sim Cl2 \\sim Cl1 \\sim C125: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
F1B \\sim F2B \\sim F3B \\sim F1A \\sim F2A \\sim F3A: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
F4 \\sim F5 \\sim F6 \\sim C87 \\sim C88 \\sim C89 \\sim C90 \\sim C91 \\sim
C92 \\sim C93: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C119 \\sim C120 \\sim C121 \\sim C122 \\sim C123 \\sim C124: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C128) \\sim Ueq, Uanis(C127) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C126) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C137) \\sim Ueq, Uanis(C96) \\sim Ueq, Uanis(C138) \\sim Ueq, Uanis(C139)
\\sim Ueq, Uanis(C140) \\sim Ueq, Uanis(C141) \\sim Ueq, Uanis(C142) \\sim Ueq,
Uanis(Cl8) \\sim Ueq, Uanis(Cl7) \\sim Ueq, Uanis(C128) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(F1B) \\sim Ueq, Uanis(F2B) \\sim Ueq, Uanis(F3B) \\sim Ueq, Uanis(C25)
\\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(F2A) \\sim Ueq, Uanis(F3A) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C71) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C83) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C9) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C78) \\sim Ueq, Uanis(C79) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
Uanis(C82) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C85)
\\sim Ueq, Uanis(N86) \\sim Ueq, Uanis(C81) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(C82) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
6. Others
 Sof(C57B)=Sof(C58B)=Sof(H58B)=Sof(C59B)=Sof(H59B)=Sof(C60B)=Sof(H60B)=
 Sof(C61B)=Sof(H61B)=Sof(C62B)=Sof(H62B)=1-FVAR(1)
 Sof(C57A)=Sof(C58A)=Sof(H58A)=Sof(C59A)=Sof(H59A)=Sof(C60A)=Sof(H60A)=
 Sof(C61A)=Sof(H61A)=Sof(C62A)=Sof(H62A)=FVAR(1)
 Sof(F1B)=Sof(F2B)=Sof(F3B)=1-FVAR(2)
 Sof(F1A)=Sof(F2A)=Sof(F3A)=FVAR(2)
 Fixed Sof: C130(0.25) H13A(0.25) H13B(0.25) H13C(0.25) C131(0.25) C132(0.25)
 H132(0.25) C133(0.25) H133(0.25) C134(0.25) H134(0.25) C135(0.25) H135(0.25)
 C136(0.25) H136(0.25) C137(0.25) H13D(0.25) H13E(0.25) H13F(0.25) C96(0.25)
 C138(0.25) H138(0.25) C139(0.25) H139(0.25) C140(0.25) H140(0.25) C141(0.25)
 H141(0.25) C142(0.25) H142(0.25) C143(0.25) H14A(0.25) H14B(0.25) H14C(0.25)
 C144(0.25) C145(0.25) H145(0.25) C146(0.25) H146(0.25) C147(0.25) H147(0.25)
 C148(0.25) H148(0.25) C149(0.25) H149(0.25) Cl5(0.25) Cl6(0.25) C127(0.25)
 H12A(0.25) H12B(0.25) Cl10(0.25) Cl9(0.25) C129(0.25) H12C(0.25) H12D(0.25)
 Cl4(0.5) Cl3(0.5) C126(0.5) H12E(0.5) H12F(0.5) Cl2(0.25) Cl1(0.25) C125(0.25)
 H12G(0.25) H12H(0.25) Cl8(0.25) Cl7(0.25) C128(0.25) H12I(0.25) H12J(0.25)
7.a Free rotating group:
 C130(C131,C132,C133,C134,C135,C136), C137(C96,C138,C139,C140,C141,C142),
 C143(C144,C145,C146,C147,C148,C149,P1,F7,F8,F9,F10,F11,F12,P4,F25,F26,F27,F28,
 F29,F30,P2,F13,F14,F15,F16,F17,F18,P3,F19,F20,F21,F22,F23,F24), Cl5(Cl6,C127),
 Cl10(Cl9,C129), Cl4(Cl3,C126), Cl2(Cl1,C125), Cl8(Cl7,C128,F1A,F2A,F3A)
7.b Secondary CH2 refined with riding coordinates:
 C127(H12A,H12B), C129(H12C,H12D), C126(H12E,H12F), C125(H12G,H12H), C128(H12I,
 H12J)
7.c Me refined with riding coordinates:
 C130(H13A,H13B,H13C), C137(H13D,H13E,H13F), C143(H14A,H14B,H14C)
7.d Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C20(H20), C21(H21), C22(H22), C23(H23),
 C2(H2), C3(H3), C4(H4), C5(H5), C14(H14), C15(H15), C16(H16), C17(H17),
 C27(H27), C28(H28), C30(H30), C31(H31), C33(H33), C36(H36), C37(H37), C40(H40),
  C42(H42), C43(H43), C45(H45), C46(H46), C48(H48), C49(H49), C52(H52),
 C53(H53), C54(H54), C55(H55), C56(H56), C58B(H58B), C59B(H59B), C60B(H60B),
 C61B(H61B), C62B(H62B), C58A(H58A), C59A(H59A), C60A(H60A), C61A(H61A),
 C62A(H62A), C70(H70), C71(H71), C72(H72), C73(H73), C64(H64), C65(H65),
 C66(H66), C67(H67), C76(H76), C77(H77), C78(H78), C79(H79), C85(H85), C82(H82),
  C83(H83), C84(H84), C89(H89), C90(H90), C92(H92), C93(H93), C95(H95),
 C98(H98), C99(H99), C102(H102), C104(H104), C105(H105), C107(H107), C108(H108),
  C110(H110), C111(H111), C114(H114), C115(H115), C116(H116), C117(H117),
 C118(H118), C120(H120), C121(H121), C122(H122), C123(H123), C124(H124),
 C132(H132), C133(H133), C134(H134), C135(H135), C136(H136), C138(H138),
 C139(H139), C140(H140), C141(H141), C142(H142), C145(H145), C146(H146),
 C147(H147), C148(H148), C149(H149)
7.e Fitted hexagon refined as free rotating group:
 N12(C7,C8,C9,C10,C11), N24(C19,C20,C21,C22,C23), C57B(C58B,C59B,C60B,C61B,
 C62B), C57A(C58A,C59A,C60A,C61A,C62A), N74(C69,C70,C71,C72,C73), C85(N86,C81,
 C82,C83,C84)
;
_shelx_res_checksum              69085
_shelx_hkl_checksum              31659
_olex2_exptl_crystal_mounting_method 'mounted in oil on a MiTeGen microloop'
_olex2_submission_original_sample_id LH534Ru
_olex2_submission_special_instructions 'No special instructions were received'