Azadipyrromethene cyclometalation in neutral Ru(II) complexes: photosensitizers with extended near-infrared absorption for solar energy conversion applications.
Bessette, André; Cibian, Mihaela; Ferreira, Janaina G.; DiMarco, Brian N.; Bélanger, Francis; Désilets, Denis; Meyer, Gerald J.; Hanan, Garry S.; Dalton transactions (Cambridge, England : 2003) 45 (2016) 10563–10576; doi:10.1039/c6dt00961a

data_7039478
_publ_section_title
;
 Azadipyrromethene cyclometalation in neutral Ru(II) complexes:
 photosensitizers with extended near-infrared absorption for solar energy
 conversion applications.
;
_journal_issue                   26
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10563
_journal_page_last               10576
_journal_paper_doi               10.1039/c6dt00961a
_journal_volume                  45
_journal_year                    2016
_chemical_formula_moiety         'C57 H43 Br N6 O4 Ru, 0.5(C7 H8)'
_chemical_formula_sum            'C60.5 H47 Br N6 O4 Ru'
_chemical_formula_weight         1103.02
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2015-02-07
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.19 svn.r3143 for OlexSys, GUI svn.r4992)
;
_audit_update_record
;
2015-08-18 deposited with the CCDC.
2016-05-19 downloaded from the CCDC.
;
_cell_angle_alpha                73.36(3)
_cell_angle_beta                 70.90(3)
_cell_angle_gamma                73.29(3)
_cell_formula_units_Z            2
_cell_length_a                   12.207(2)
_cell_length_b                   13.408(3)
_cell_length_c                   16.302(3)
_cell_measurement_reflns_used    9996
_cell_measurement_temperature    100
_cell_measurement_theta_max      60.581
_cell_measurement_theta_min      2.546
_cell_volume                     2359.7(10)
_computing_cell_refinement       'SAINT v8.30c (Bruker AXS, 2013)'
_computing_data_collection       'APEX2 v2013.4 (Bruker AXS, 2013)'
_computing_data_reduction        'SAINT v8.30c (Bruker AXS, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector_area_resol_mean 10.24
_diffrn_measured_fraction_theta_full 0.957
_diffrn_measured_fraction_theta_max 0.923
_diffrn_measurement_device_type  'Bruker D8 VENTURE diffractometer'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.3418
_diffrn_reflns_av_R_equivalents  0.0714
_diffrn_reflns_av_unetI/netI     0.0873
_diffrn_reflns_Laue_measured_fraction_full 0.957
_diffrn_reflns_Laue_measured_fraction_max 0.923
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            42720
_diffrn_reflns_point_group_measured_fraction_full 0.957
_diffrn_reflns_point_group_measured_fraction_max 0.923
_diffrn_reflns_theta_full        53.618
_diffrn_reflns_theta_max         61.293
_diffrn_reflns_theta_min         2.554
_diffrn_source                   'Metal Jet'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.789
_exptl_absorpt_correction_T_max  0.7519
_exptl_absorpt_correction_T_min  0.6322
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1452 before and 0.0686 after correction.
The Ratio of minimum to maximum transmission is 0.8408.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.552
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             1126
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: '
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.025
_exptl_crystal_size_min          0.025
_refine_diff_density_max         1.609
_refine_diff_density_min         -1.022
_refine_diff_density_rms         0.135
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     813
_refine_ls_number_reflns         10177
_refine_ls_number_restraints     1274
_refine_ls_restrained_S_all      0.973
_refine_ls_R_factor_all          0.1233
_refine_ls_R_factor_gt           0.0768
_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^)+(0.0818P)^2^+9.8263P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1666
_refine_ls_wR_factor_ref         0.1911
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6854
_reflns_number_total             10177
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6dt00961a2.cif
_cod_data_source_block           udm22_0m_a
_cod_depositor_comments
'Adding full bibliography for 7039476--7039478.cif.'
_cod_original_cell_volume        2359.8(10)
_cod_original_formula_sum        'C60.50 H47 Br N6 O4 Ru'
_cod_database_code               7039478
_shelxl_version_number           2014/6
_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
2. Restrained distances
 C1S-C2S
 1.507 with sigma of 0.001
 C8A-O1A \\sim C8B-O1B
 with sigma of 0.001
 O1B-C33B \\sim O1A-C33A
 with sigma of 0.001
 C30A-O4A \\sim C30B-O4B
 with sigma of 0.001
 O4A-C36A \\sim O4B-C36B
 with sigma of 0.001
 O3A-C35A \\sim O3B-C35B
 with sigma of 0.001
 C24A-O3A \\sim C24B-O3B
 with sigma of 0.001
 C20-C27B \\sim C20-C27A
 with sigma of 0.001
 C18-C21A \\sim C18-C21B
 with sigma of 0.001
 C2-C5A \\sim C2-C5B
 with sigma of 0.001
 C27A-C28A \\sim C27A-C32A \\sim C27B-C28B \\sim C27B-C32B
 with sigma of 0.001
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.5A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(C1S) \\sim Ueq, Uanis(C2S) \\sim Ueq, Uanis(C3S) \\sim Ueq, Uanis(C4S)
\\sim Ueq, Uanis(C5S) \\sim Ueq, Uanis(C6S) \\sim Ueq, Uanis(C7S) \\sim Ueq:
with sigma of 0.02 and sigma for terminal atoms of 0.04
5. Rigid body (RIGU) restrains
 C32B, C28B, C30B, C31B, C29B, C27A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: O1A(0.4) O1B(0.6) O3A(0.55) O4A(0.7) O4B(0.3) C5B(0.6) C6B(0.6)
 H6B(0.6) C7B(0.6) H7B(0.6) C8B(0.6) C9B(0.6) H9B(0.6) C10B(0.6) H10B(0.6)
 C5A(0.4) C6A(0.4) H6A(0.4) C7A(0.4) H7A(0.4) C8A(0.4) C9A(0.4) H9A(0.4)
 C10A(0.4) H10A(0.4) C21A(0.55) C26A(0.55) H26A(0.55) C25A(0.55) H25A(0.55)
 C24A(0.55) C23A(0.55) H23A(0.55) C22A(0.55) H22A(0.55) C21B(0.45) C26B(0.45)
 H26B(0.45) C25B(0.45) H25B(0.45) C24B(0.45) C23B(0.45) H23B(0.45) C22B(0.45)
 H22B(0.45) C27B(0.3) C28A(0.7) H28A(0.7) C29A(0.7) H29A(0.7) C30A(0.7)
 C31A(0.7) H31A(0.7) C32A(0.7) H32A(0.7) C27A(0.7) C32B(0.3) H32B(0.3)
 C31B(0.3) H31B(0.3) C30B(0.3) C29B(0.3) H29B(0.3) C28B(0.3) H28B(0.3)
 C33A(0.6) H33A(0.6) H33B(0.6) H33C(0.6) C33B(0.4) H33D(0.4) H33E(0.4)
 H33F(0.4) C36A(0.7) H36A(0.7) H36B(0.7) H36C(0.7) C36B(0.3) H36D(0.3)
 H36E(0.3) H36F(0.3) C2S(0.5) C3S(0.5) H3S(0.5) C4S(0.5) H4S(0.5) C5S(0.5)
 H5S(0.5) C6S(0.5) H6S(0.5) C7S(0.5) H7S(0.5) C1S(0.5) H1SA(0.5) H1SB(0.5)
 H1SC(0.5) O3B(0.45) C35B(0.45) H35A(0.45) H35B(0.45) H35C(0.45) C35A(0.55)
 H35D(0.55) H35E(0.55) H35F(0.55)
7.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C6B(H6B), C7B(H7B), C9B(H9B), C10B(H10B), C6A(H6A), C7A(H7A),
 C9A(H9A), C10A(H10A), C13(H13), C15(H15), C16(H16), C19(H19), C26A(H26A),
 C25A(H25A), C23A(H23A), C22A(H22A), C26B(H26B), C25B(H25B), C23B(H23B),
 C22B(H22B), C28A(H28A), C29A(H29A), C31A(H31A), C32A(H32A), C32B(H32B),
 C31B(H31B), C29B(H29B), C28B(H28B), C38(H38), C39(H39), C40(H40), C41(H41),
 C43(H43), C45(H45), C48(H48), C49(H49), C50(H50), C51(H51), C53(H53), C54(H54),
  C56(H56), C57(H57), C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S), C7S(H7S)
7.b Fitted hexagon refined as free rotating group:
 C5B(C6B,C7B,C8B,C9B,C10B), C5A(C6A,C7A,C8A,C9A,C10A), C11(C12,C13,C14,C15,
 C16), C21A(C26A,C25A,C24A,C23A,C22A), C21B(C26B,C25B,C24B,C23B,C22B),
 C27B(C28A,C29A,C30A,C31A,C32A), C27A(C32B,C31B,C30B,C29B,C28B), C2S(C3S,C4S,
 C5S,C6S,C7S)
7.c Idealised Me refined as rotating group:
 C33A(H33A,H33B,H33C), C33B(H33D,H33E,H33F), C34(H34A,H34B,H34C), C36A(H36A,
 H36B,H36C), C36B(H36D,H36E,H36F), C1S(H1SA,H1SB,H1SC), C35B(H35A,H35B,H35C),
 C35A(H35D,H35E,H35F)
;
_olex2_submission_special_instructions 'No special instructions were received'