Cyclometalated Ir-Zr Metal-Organic Frameworks as Recyclable Visible-Light Photocatalysts for Sulfide Oxidation into Sulfoxide in Water.
Wei, Lian-Qiang; Ye, Bao-Hui; ACS applied materials & interfaces  (2019) –; doi:10.1021/acsami.9b15646

data_4514431
_publ_section_title
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 Cyclometalated Ir-Zr Metal-Organic Frameworks as Recyclable Visible-Light
 Photocatalysts for Sulfide Oxidation into Sulfoxide in Water.
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_journal_name_full               'ACS applied materials &amp; interfaces'
_journal_paper_doi               10.1021/acsami.9b15646
_journal_year                    2019
_chemical_formula_moiety         'C44 H32 Ir N4 O4, 2(C H Cl3), Cl'
_chemical_formula_sum            'C46 H34 Cl7 Ir N4 O4'
_chemical_formula_weight         1147.12
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     heavy
_audit_creation_date             2019-03-31
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.290(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.7903(6)
_cell_length_b                   21.5052(13)
_cell_length_c                   19.8216(13)
_cell_measurement_reflns_used    4065
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      62.3040
_cell_measurement_theta_min      3.9130
_cell_volume                     5642.4(6)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini ultra'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0880
_diffrn_reflns_av_unetI/netI     0.0789
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            28908
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        65.059
_diffrn_reflns_theta_max         65.059
_diffrn_reflns_theta_min         3.339
_exptl_absorpt_coefficient_mu    7.950
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.16982
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.350
_exptl_crystal_description       block
_exptl_crystal_F_000             2264
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.07
_refine_diff_density_max         5.470
_refine_diff_density_min         -1.881
_refine_diff_density_rms         0.286
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.074
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     489
_refine_ls_number_reflns         9556
_refine_ls_number_restraints     108
_refine_ls_restrained_S_all      1.096
_refine_ls_R_factor_all          0.1268
_refine_ls_R_factor_gt           0.1052
_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^)+(0.2500P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3047
_refine_ls_wR_factor_ref         0.3411
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6862
_reflns_number_total             9556
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            am9b15646_si_002.cif
_cod_data_source_block           1
_cod_database_code               4514431
_shelx_shelxl_version_number     2014/7
_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
 Cl3-C45
 1.74 with sigma of 0.01
 Cl4-C45 = Cl2-C45
 1.74 with sigma of 0.01
 Cl6-C46 = Cl7-C46 = Cl5-C46
 1.74 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O4) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(O1) \\sim
Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C17) \\sim Ueq, Uanis(C34) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Cl1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C22) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl4) \\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(C45)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl6) \\sim Ueq, Uanis(Cl5) \\sim Ueq, Uanis(Cl7) \\sim Ueq, Uanis(C46)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C45(H45), C46(H46)
4.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C2(H2), C3(H3), C4(H4), C5(H5), C15(H15), C12(H12), C13(H13),
 C14(H14), C25(H25), C19(H19), C20(H20), C21(H21), C22(H22), C29(H29), C30(H30),
  C31(H31), C32(H32), C38(H38), C35(H35), C36(H36), C37(H37), C43(H43),
 C44(H44), C41(H41), C42(H42)
4.c Fitted hexagon refined as free rotating group:
 C1(N1,C9,C8,C7,C6), C15(C10,C11,C12,C13,C14), C18(N2,C26,C25,C24,C23),
 C28(C29,C30,C31,C32,C27), C38(C39,N3,C35,C36,C37), C43(C44,N4,C40,C41,C42)
4.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C34(H34A,H34B,H34C)
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