Synthesis, crystal structures, photophysical, electrochemical studies, DFT and TD-DFT calculations and Hirshfeld analysis of new 2,2′:6′,2′′-terpyridine ligands with pendant 4′-(trimethoxyphenyl) groups and their homoleptic ruthenium complexes
Ramesh, Golla; P., Raghavendra Kumar; Pillegowda, Manohar; Periyasamy, Ganga; Suchetan, P. A.; Butcher, R. J.; Foro, Sabine; Nagaraju, G.; New Journal of Chemistry 44 (2020) 11471–11489; doi:10.1039/D0NJ00046A

data_7059729
_publ_section_title
;
 Synthesis, crystal structures, photophysical, electrochemical studies,
 DFT and TD-DFT calculations and Hirshfeld analysis of new
 2,2&#x2032;:6&#x2032;,2&#x2032;&#x2032;-terpyridine ligands with pendant
 4&#x2032;-(trimethoxyphenyl) groups and their homoleptic ruthenium
 complexes
;
_journal_issue                   27
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              11471
_journal_page_last               11489
_journal_paper_doi               10.1039/D0NJ00046A
_journal_volume                  44
_journal_year                    2020
_chemical_formula_moiety         'C48 H42 N6 O6 Ru, 2(F6 P), 2(H2 O)'
_chemical_formula_sum            'C48 H46 F12 N6 O8 P2 Ru'
_chemical_formula_weight         1225.92
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2020-06-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-06-02 deposited with the CCDC.	2020-06-10 downloaded from the CCDC.
;
_cell_angle_alpha                105.131(4)
_cell_angle_beta                 95.341(4)
_cell_angle_gamma                101.205(4)
_cell_formula_units_Z            2
_cell_length_a                   11.4094(5)
_cell_length_b                   12.1354(6)
_cell_length_c                   19.0576(8)
_cell_measurement_reflns_used    29661
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      31.6800
_cell_measurement_theta_min      1.7580
_cell_volume                     2469.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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      100.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.940
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction Gemini Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0959
_diffrn_reflns_av_unetI/netI     0.0570
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.940
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            63674
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.742
_diffrn_reflns_theta_min         1.785
_diffrn_source                   'fine-focus sealed X-ray tube'
_exptl_absorpt_coefficient_mu    0.489
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73367
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.649
_exptl_crystal_description       prism
_exptl_crystal_F_000             1244
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.473
_refine_diff_density_min         -1.907
_refine_diff_density_rms         0.166
_refine_ls_extinction_coef       0.0142(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/1 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     828
_refine_ls_number_reflns         15758
_refine_ls_number_restraints     231
_refine_ls_restrained_S_all      1.267
_refine_ls_R_factor_all          0.0869
_refine_ls_R_factor_gt           0.0756
_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^)+(0.0964P)^2^+6.1125P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1841
_refine_ls_wR_factor_ref         0.1919
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13792
_reflns_number_total             15758
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0nj00046a2.cif
_cod_data_source_block           I_Global_rk236
_cod_depositor_comments
;Adding full bibliography for 7059727--7059730.cif.

 Adding full bibliography for 7059727--7059730.cif.
;
_cod_database_code               7059729
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.957
_shelx_estimated_absorpt_t_min   0.904
_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 O(H,H) groups
2. Restrained distances
 P1-F11 = P1-F12 = P1-F13 = P1-F14 = P1-F15 = P1-F16
 1.39077 with sigma of 0.02
 F11-F12 = F11-F13 = F11-F14 = F11-F15 = F16-F12 = F16-F13 = F16-F13 = F16-F14
 2.408814 with sigma of 0.02
 F12-F13 = F13-F14 = F14-F15
 2.408814 with sigma of 0.02
 F11-F16 = F12-F14 = F13-F15
 2.78154 with sigma of 0.02
 P1-F11A = P1-F12A = P1-F13A = P1-F14A = P1-F15A = P1-F16A
 1.39077 with sigma of 0.02
 F11A-F12A = F11A-F13A = F11A-F14A = F11A-F15A = F16A-F12A = F16A-F13A
 2.408814 with sigma of 0.02
 F16A-F13A = F16A-F14A
 2.408814 with sigma of 0.02
 F12A-F13A = F13A-F14A = F14A-F15A
 2.408814 with sigma of 0.02
 F11A-F16A = F12A-F14A = F13A-F15A
 2.78154 with sigma of 0.02
 P2-F21 = P2-F22 = P2-F23
 1.39077 with sigma of 0.02
 F21-F22 = F21-F23 = F22-F23
 2.408814 with sigma of 0.02
 P2-F21A = P2-F22A = P2-F23A
 1.39077 with sigma of 0.02
 F21A-F22A = F21A-F23A = F22A-F23A
 2.408814 with sigma of 0.02
 P3-F31 = P3-F32 = P3-F33
 1.39077 with sigma of 0.02
 F31-F32 = F31-F33 = F32-F33
 2.408814 with sigma of 0.02
 P3-F31A = P3-F32A = P3-F33A
 1.39077 with sigma of 0.02
 F31A-F32A = F31A-F33A = F32A-F33A
 2.408814 with sigma of 0.02
 O1W-H1WA = O1W-H1WB
 0.82 with sigma of 0.02
 H1WA-H1WB
 1.297 with sigma of 0.02
 O2WA-H2WA = O2WA-H2WB
 0.82 with sigma of 0.02
 H2WA-H2WB
 1.297 with sigma of 0.02
 O2WB-H2WC = O2WB-H2WD
 0.82 with sigma of 0.02
 H2WC-H2WD
 1.297 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O1AA \\sim O1AB \\sim C22A \\sim C22C: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01
F11 \\sim F11A \\sim F12 \\sim F12A \\sim F13 \\sim F13A \\sim F14 \\sim F14A
\\sim F15 \\sim F15A \\sim F16 \\sim F16A: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01
F21 \\sim F21A \\sim F22 \\sim F22A \\sim F23 \\sim F23A: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02
O2WA \\sim O2WB: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
Uanis(F31) = Uanis(F31A)
Uanis(F32) = Uanis(F32A)
Uanis(F33) = Uanis(F33A)
4. Same fragment restrains
{O1AA, C22A} sigma for 1-2: 0.005, 1-3: 0.04
as
{O1AB, C22C}
5. Others
 Sof(F11A)=Sof(F12A)=Sof(F13A)=Sof(F14A)=Sof(F15A)=Sof(F16A)=1-FVAR(1)
 Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(F16)=FVAR(1)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=FVAR(2)
 1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1(DFIX)=1.732*
 FVAR(3)
 1(DFIX)=1(DFIX)=2*FVAR(3)
 Sof(F21A)=Sof(F22A)=Sof(F23A)=1-FVAR(3)
 Sof(F21)=Sof(F22)=Sof(F23)=FVAR(3)
 Sof(O1AB)=Sof(C22C)=Sof(H22A)=Sof(H22B)=Sof(H22C)=1-FVAR(4)
 Sof(O1AA)=Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=FVAR(4)
 Sof(O2WB)=Sof(H2WC)=Sof(H2WD)=1-FVAR(5)
 Sof(O2WA)=Sof(H2WA)=Sof(H2WB)=FVAR(5)
 Sof(F31A)=Sof(F32A)=Sof(F33A)=1-FVAR(6)
 Sof(F31)=Sof(F32)=Sof(F33)=FVAR(6)
6.a Riding coordinates:
 O1W(H1WA,H1WB), O2WA(H2WA,H2WB), O2WB(H2WC,H2WD)
6.b Aromatic/amide H refined with riding coordinates:
 C1A(H1A), C1B(H1B), C2A(H2A), C2B(H2B), C3A(H3A), C3B(H3B), C4A(H4A),
 C4B(H4B), C7A(H7A), C7B(H7B), C9A(H9A), C9B(H9B), C12A(H12A), C12B(H12B),
 C13A(H13A), C13B(H13B), C14A(H14A), C14B(H14B), C15A(H15A), C15B(H15B),
 C17A(H17A), C18B(H18B), C20A(H20A), C21B(H21B)
6.c Idealised Me refined as rotating group:
 C22C(H22A,H22B,H22C), C22A(H22D,H22E,H22F), C22B(H22G,H22H,H22I), C23A(H23A,
 H23B,H23C), C23B(H23D,H23E,H23F), C24A(H24A,H24B,H24C), C24B(H24D,H24E,H24F)
;
_shelx_res_checksum              82513
_olex2_exptl_crystal_mounting_method 'Polymer Loop'
_olex2_submission_special_instructions 'No special instructions were received'