Sterically hindered Re- and Mn-CO<sub>2</sub> reduction catalysts for solar energy conversion.
Shipp, James D.; Carson, Heather; Spall, Steven J. P.; Parker, Simon C.; Chekulaev, Dimitri; Jones, Natalie; Mel'nikov, Mikhail Ya; Robertson, Craig C.; Meijer, Anthony J. H. M.; Weinstein, Julia A.; Dalton transactions (Cambridge, England : 2003) 49 (2020) 4230–4243; doi:10.1039/d0dt00252f

data_7703567
_publ_section_title
;
 Sterically hindered Re- and Mn-CO<sub>2</sub> reduction catalysts for
 solar energy conversion.
;
_journal_issue                   14
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              4230
_journal_page_last               4243
_journal_paper_doi               10.1039/d0dt00252f
_journal_volume                  49
_journal_year                    2020
_chemical_formula_moiety         'C43 H50 Br Mn N4 O5, 0.5(C4 H10 O)'
_chemical_formula_sum            'C45 H55 Br Mn N4 O5.5'
_chemical_formula_weight         874.78
_chemical_properties_physical    Light-sensitive,Photo-sensitive
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-09
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2019.08.16 svn.r3652 for OlexSys, GUI svn.r5895)
;
_audit_update_record
;
2019-09-12 deposited with the CCDC.	2020-02-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.379(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.8147(12)
_cell_length_b                   16.2939(11)
_cell_length_c                   17.9380(11)
_cell_measurement_reflns_used    9900
_cell_measurement_temperature    110.01
_cell_measurement_theta_max      24.61
_cell_measurement_theta_min      2.37
_cell_volume                     4434.7(5)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2016)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2016)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL n/a (Sheldrick, 2008)'
_computing_structure_solution    'XT n/a (Sheldrick, 2015)'
_diffrn_ambient_temperature      110.01
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1106
_diffrn_reflns_av_unetI/netI     0.1125
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            76332
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.643
_diffrn_reflns_theta_min         1.342
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.247
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4632
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1079 before and 0.0828 after correction.
The Ratio of minimum to maximum transmission is 0.6212.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'dark orange'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.310
_exptl_crystal_description       plate
_exptl_crystal_F_000             1828
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.187
_exptl_crystal_size_min          0.083
_refine_diff_density_max         1.602
_refine_diff_density_min         -0.895
_refine_diff_density_rms         0.132
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     551
_refine_ls_number_reflns         10219
_refine_ls_number_restraints     531
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.1961
_refine_ls_R_factor_gt           0.0947
_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^)+(0.0961P)^2^+25.8920P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2175
_refine_ls_wR_factor_ref         0.2798
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5265
_reflns_number_total             10219
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0dt00252f2.cif
_cod_data_source_block           ch1jw286s_0m
_cod_depositor_comments
'Adding full bibliography for 7703566--7703567.cif.'
_cod_original_formula_sum        'C45 H55 Br Mn N4 O5.50'
_cod_database_code               7703567
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.904
_shelx_estimated_absorpt_t_min   0.655
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C24B-C23B \\sim C24B-C23A \\sim C22-C23A \\sim C22-C23B \\sim C21B-C22 \\sim
C21A-C22 \\sim C21A-C20
 \\sim C21B-C20 \\sim C24B-C25B \\sim C24A-C25A
 with sigma of 0.02
 C4S-C3S \\sim C2S-C1S
 with sigma of 0.02
 O1S-C3S \\sim O1S-C2S
 with sigma of 0.02
 C4S-O1S \\sim O1S-C1S
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O1S \\sim C1S \\sim C2S \\sim C3S \\sim C4S: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Uanis(C24B) = Uanis(C25B) = Uanis(C24A) = Uanis(C25A) = Uanis(C23B) =
Uanis(C23A) = Uanis(C22)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H27C)=Sof(H27D)=Sof(C28B)=Sof(H28D)=Sof(H28E)=Sof(H28F)=1-FVAR(1)
 Sof(H27A)=Sof(H27B)=Sof(C28A)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(1)
 Sof(H20C)=Sof(H20D)=Sof(H22C)=Sof(H22D)=Sof(C21B)=Sof(H21C)=Sof(H21D)=
 Sof(C23B)=Sof(H23C)=Sof(H23D)=Sof(C24B)=Sof(H24C)=Sof(H24D)=Sof(C25B)=
 Sof(H25D)=Sof(H25E)=Sof(H25F)=1-FVAR(2)
 Sof(H20A)=Sof(H20B)=Sof(H22A)=Sof(H22B)=Sof(C21A)=Sof(H21A)=Sof(H21B)=
 Sof(C23A)=Sof(H23A)=Sof(H23B)=Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(C25A)=
 Sof(H25A)=Sof(H25B)=Sof(H25C)=FVAR(2)
 Fixed Sof: O1S(0.5) C1S(0.5) H1SA(0.5) H1SB(0.5) H1SC(0.5) C2S(0.5) H2SB(0.5)
 H2SA(0.5) C3S(0.5) H3SB(0.5) H3SA(0.5) C4S(0.5) H4SA(0.5) H4SB(0.5) H4SC(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C20(H20A,H20B), C20(H20C,H20D), C22(H22A,H22B), C22(H22C,
 H22D), C27(H27C,H27D), C27(H27A,H27B), C35(H35A,H35B), C36(H36A,H36B),
 C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C21A(H21A,H21B), C23A(H23A,
 H23B), C24A(H24A,H24B), C21B(H21C,H21D), C23B(H23C,H23D), C24B(H24C,H24D),
 C2S(H2SB,H2SA), C3S(H3SB,H3SA)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C7(H7), C8(H8), C9(H9), C15(H15), C16(H16), C18(H18),
 C19(H19), C30(H30), C31(H31), C33(H33), C34(H34)
6.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C40(H40A,H40B,H40C), C25A(H25A,H25B,H25C), C28A(H28A,
 H28B,H28C), C25B(H25D,H25E,H25F), C28B(H28D,H28E,H28F), C1S(H1SA,H1SB,H1SC),
 C4S(H4SA,H4SB,H4SC)
;
_shelx_res_checksum              8712
_olex2_exptl_crystal_mounting_method 'Mitigen microloop in fomblin oil'
_olex2_submission_special_instructions 'No special instructions were received'