Ruthenium(iv) N-confused porphyrin μ-oxo-bridged dimers: acid-responsive molecular rotors
Iwanaga, Osamu; Fukuyama, Kazuki; Mori, Shigeki; Song, Jun Tae; Ishihara, Tatsumi; Miyazaki, Takaaki; Ishida, Masatoshi; Furuta, Hiroyuki; RSC Advances 11 (2021) 24575–24579; doi:10.1039/D1RA05063J

data_7243205
_publ_section_title
;
 Ruthenium(iv) N-confused porphyrin \m-oxo-bridged dimers: acid-responsive
 molecular rotors
;
_journal_issue                   40
_journal_name_full               'RSC Advances'
_journal_page_first              24575
_journal_page_last               24579
_journal_paper_doi               10.1039/D1RA05063J
_journal_volume                  11
_journal_year                    2021
_chemical_formula_moiety         'C88 H53 N8 O3 Ru2, 5(C1 H1 Cl3)'
_chemical_formula_sum            'C93 H58 Cl15 N8 O3 Ru2'
_chemical_formula_weight         2069.36
_chemical_name_systematic        Ru2-3
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-02-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2021-04-08 deposited with the CCDC.	2021-07-05 downloaded from the CCDC.
;
_cell_angle_alpha                78.272(2)
_cell_angle_beta                 79.906(2)
_cell_angle_gamma                82.497(2)
_cell_formula_units_Z            2
_cell_length_a                   13.0869(3)
_cell_length_b                   18.3474(4)
_cell_length_c                   18.8229(4)
_cell_measurement_reflns_used    42586
_cell_measurement_temperature    100
_cell_measurement_theta_max      31.3420
_cell_measurement_theta_min      1.8350
_cell_volume                     4335.54(17)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection
'CrystalClear-SM Expert 2.1 b46 (Rigaku, 2016)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100
_diffrn_detector                 CCD
_diffrn_detector_area_resol_mean 7.111
_diffrn_detector_type            'Rigaku Saturn724+ area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -110.00  70.00   0.50    4.00    --  -20.00  45.00  90.00  360
  2  \w   -110.00  70.00   0.50    4.00    --  -20.00  45.00 180.00  360
  3  \w   -110.00  70.00   0.50    4.00    --  -20.00  45.00 270.00  360
  4  \w   -110.00  70.00   0.50    4.00    --  -20.00  45.00   0.00  360
;
_diffrn_measurement_device_type  'Rigaku Varimax with Saturn'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0315171000
_diffrn_orient_matrix_UB_12      0.0343577000
_diffrn_orient_matrix_UB_13      -0.0072921000
_diffrn_orient_matrix_UB_21      -0.0442862000
_diffrn_orient_matrix_UB_22      -0.0198158000
_diffrn_orient_matrix_UB_23      0.0038036000
_diffrn_orient_matrix_UB_31      -0.0102835000
_diffrn_orient_matrix_UB_32      0.0010600000
_diffrn_orient_matrix_UB_33      0.0380678000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0550
_diffrn_reflns_av_unetI/netI     0.0569
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            74535
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.999
_diffrn_reflns_theta_min         1.588
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'MicroMax 007'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.868
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92205
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.585
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2078
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: CHCl3/hexane'
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.459
_refine_diff_density_min         -1.156
_refine_diff_density_rms         0.110
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1201
_refine_ls_number_reflns         20907
_refine_ls_number_restraints     378
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0780
_refine_ls_R_factor_gt           0.0557
_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^)+(0.0445P)^2^+13.6878P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1236
_refine_ls_wR_factor_ref         0.1318
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16163
_reflns_number_total             20907
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ra05063j2.cif
_cod_data_source_block           proffuruta_CCDC1
_cod_database_code               7243205
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C88 H54 N8 O3 Ru2'
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.958
_reflns_odcompleteness_completeness 90.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.25
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Shared sites
{N4, C119}
{C19, N104}
{N8, C163}
{C63, N108}
3. Restrained distances
 Cl4-C90 = Cl5-C90 = Cl6-C90
 1.78 with sigma of 0.02
 Cl1-C89 = Cl2-C89 = Cl3-C89
 1.78 with sigma of 0.02
 Cl34-C190 = Cl35-C190 = Cl36-C190
 1.78 with sigma of 0.02
 Cl31-C189 = Cl32-C189 = Cl33-C189
 1.78 with sigma of 0.02
 Cl10-C92 = Cl11-C92 = Cl12-C92
 1.78 with sigma of 0.02
 Cl40-C192 = Cl41-C192 = Cl42-C192
 1.78 with sigma of 0.02
 Cl1-Cl2 = Cl2-Cl3 = Cl3-Cl1
 2.85 with sigma of 0.04
 Cl4-Cl5 = Cl5-Cl6 = Cl6-Cl4
 2.85 with sigma of 0.04
 Cl34-Cl35 = Cl35-Cl36 = Cl36-Cl34
 2.85 with sigma of 0.04
 Cl31-Cl32 = Cl32-Cl33 = Cl33-Cl31
 2.85 with sigma of 0.04
 Cl10-Cl11 = Cl11-Cl12 = Cl12-Cl10
 2.85 with sigma of 0.04
 Cl40-Cl41 = Cl41-Cl42 = Cl42-Cl40
 2.85 with sigma of 0.04
4. Uiso/Uaniso restraints and constraints
Cl1 \\sim Cl2 \\sim Cl3 \\sim C89: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
Cl4 \\sim Cl5 \\sim Cl6 \\sim C90: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
Cl31 \\sim Cl32 \\sim Cl33 \\sim C189: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 2A
Cl34 \\sim Cl35 \\sim Cl36 \\sim C190: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 2A
Cl10 \\sim Cl11 \\sim Cl12 \\sim C92: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 2A
Cl40 \\sim Cl41 \\sim Cl42 \\sim C192: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 2A
Uanis(Cl4) \\sim Ueq, Uanis(Cl5) \\sim Ueq, Uanis(Cl6) \\sim Ueq, Uanis(C90)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(Cl1) \\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(C89)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl34) \\sim Ueq, Uanis(Cl35) \\sim Ueq, Uanis(Cl36) \\sim Ueq,
Uanis(C190) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl31) \\sim Ueq, Uanis(Cl32) \\sim Ueq, Uanis(Cl33) \\sim Ueq,
Uanis(C189) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl10) \\sim Ueq, Uanis(Cl11) \\sim Ueq, Uanis(Cl12) \\sim Ueq, Uanis(C92)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl40) \\sim Ueq, Uanis(Cl41) \\sim Ueq, Uanis(Cl42) \\sim Ueq,
Uanis(C192) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N4) = Uanis(C119)
Uanis(C19) = Uanis(N104)
Uanis(C63) = Uanis(N108)
Uanis(N8) = Uanis(C163)
5. Rigid body (RIGU) restrains
 Cl4, Cl5, Cl6, C90
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1, Cl2, Cl3, C89
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl31, Cl32, Cl33, C189
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl34, Cl35, Cl36, C190
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl10, Cl11, Cl12, C92
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl40, Cl41, Cl42, C192
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(N104)=Sof(C119)=Sof(H119)=Sof(Cl31)=Sof(Cl32)=Sof(Cl33)=Sof(C189)=
 Sof(H189)=1-FVAR(1)
 Sof(N4)=Sof(C19)=Sof(H19)=Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=Sof(C89)=Sof(H89)=FVAR(1)
 Sof(N108)=Sof(C163)=Sof(H163)=Sof(Cl34)=Sof(Cl35)=Sof(Cl36)=Sof(C190)=
 Sof(H190)=1-FVAR(2)
 Sof(N8)=Sof(C63)=Sof(H63)=Sof(Cl4)=Sof(Cl5)=Sof(Cl6)=Sof(C90)=Sof(H90)=FVAR(2)
 Sof(Cl40)=Sof(Cl41)=Sof(Cl42)=Sof(C192)=Sof(H192)=1-FVAR(3)
 Sof(Cl10)=Sof(Cl11)=Sof(Cl12)=Sof(C92)=Sof(H92)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C90(H90), C190(H190), C89(H89), C189(H189), C92(H92), C192(H192), C93(H93),
 C91(H91)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C8(H8), C12(H12), C13(H13), C22(H22), C23(H23),
 C24(H24), C25(H25), C26(H26), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32),
  C34(H34), C35(H35), C36(H36), C37(H37), C38(H38), C40(H40), C41(H41),
 C42(H42), C43(H43), C44(H44), C46(H46), C47(H47), C51(H51), C52(H52), C56(H56),
  C57(H57), C67(H67), C68(H68), C69(H69), C70(H70), C72(H72), C73(H73),
 C74(H74), C75(H75), C76(H76), C78(H78), C79(H79), C80(H80), C81(H81), C82(H82),
  C84(H84), C85(H85), C86(H86), C87(H87), C88(H88), C19(H19), C119(H119),
 C63(H63), C163(H163)
;
_shelx_res_checksum              36620
_olex2_exptl_crystal_mounting_method loop
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.109
_oxdiff_exptl_absorpt_empirical_full_min 0.916