Studying manganese carbonyl photochemistry in a permanently porous metal-organic framework.
Young, Rosemary J.; Huxley, Michael T.; Wu, Lingjun; Hart, Jack; O'Shea, James; Doonan, Christian J.; Champness, Neil R.; Sumby, Christopher J.; Chemical science 14 (2023) 9409–9417; doi:10.1039/d3sc03553k

data_1569679
_publ_section_title
;
 Studying manganese carbonyl photochemistry in a permanently porous
 metal-organic framework.
;
_journal_issue                   35
_journal_name_full               'Chemical science'
_journal_page_first              9409
_journal_page_last               9417
_journal_paper_doi               10.1039/d3sc03553k
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C40 H34.25 Mn2 N6.5 O7.5, 0.375(Br), C2 H3 N'
_chemical_formula_sum            'C42 H35.75 Br0.5 Mn2 N7.5 O7.5'
_chemical_formula_weight         915.36
_space_group_crystal_system      monoclinic
_space_group_IT_number           11
_space_group_name_Hall           '-P 2yb'
_space_group_name_H-M_alt        'P 1 21/m 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-07-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-07-09 deposited with the CCDC.	2023-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.565(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4134(13)
_cell_length_b                   33.362(4)
_cell_length_c                   12.9953(13)
_cell_measurement_reflns_used    81242
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      35.835
_cell_measurement_theta_min      1.183
_cell_volume                     5356.5(10)
_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, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.883
_diffrn_measurement_device_type  'Diamond Light Source, i19 beamline'
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.6889
_diffrn_reflns_av_R_equivalents  0.1626
_diffrn_reflns_av_unetI/netI     0.3312
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.883
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       56
_diffrn_reflns_limit_k_min       -53
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            81242
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.883
_diffrn_reflns_theta_full        24.415
_diffrn_reflns_theta_max         35.835
_diffrn_reflns_theta_min         1.183
_exptl_absorpt_coefficient_mu    0.821
_exptl_absorpt_process_details   multi-scan
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.135
_exptl_crystal_description       plate
_exptl_crystal_F_000             1871
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.005
_platon_squeeze_details
;
The structure contains large accessible voids containing acetonitrile solvate
molecules and the remaining bromide counterion (0.125 Br).  Where these are 
well defined they have been modelled.  The removed electron density (335e per
unit cell; ca. 84 electrons per ASU) corresonds to ca. 15 CH3CN molecules or 
ca. 3.75 CH3CN per ASU. 
;
_refine_diff_density_max         1.074
_refine_diff_density_min         -0.987
_refine_diff_density_rms         0.126
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.878
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     619
_refine_ls_number_reflns         24595
_refine_ls_number_restraints     74
_refine_ls_restrained_S_all      0.882
_refine_ls_R_factor_all          0.2576
_refine_ls_R_factor_gt           0.1209
_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^)+(0.1517P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3187
_refine_ls_wR_factor_ref         0.3530
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7008
_reflns_number_total             24595
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc03553k2.cif
_cod_data_source_block           2_3
_cod_depositor_comments
'Adding full bibliography for 1569673--1569679.cif.'
_cod_original_cell_volume        5356.4(10)
_cod_original_formula_sum        'C42 H35.75 Br0.50 Mn2 N7.50 O7.50'
_cod_database_code               1569679
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.996
_shelx_estimated_absorpt_t_min   0.922
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Mn1-O1
 2.95 with sigma of 0.02
 Mn1-N1
 2.2 with sigma of 0.02
 Mn1-O2
 2.95 with sigma of 0.02
 N1-C3
 1.15 with sigma of 0.02
 C3-C4
 1.45 with sigma of 0.02
 Mn1-C1
 1.8 with sigma of 0.02
 C13-C14A \\sim C13-C14B
 with sigma of 0.02
 C13-C13A \\sim C13-C13B
 with sigma of 0.02
 C11-C12A \\sim C11-C12B
 with sigma of 0.02
 C13A-C12A \\sim C13B-C12B
 with sigma of 0.02
 C13-C12A \\sim C13-C12B
 with sigma of 0.04
 C11-C14A \\sim C11-C14B
 with sigma of 0.04
 C11-C13A \\sim C11-C13B
 with sigma of 0.04
3. Restrained planarity
 C12A, C11, C15A, C14A, C13, C13A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Mn1 \\sim C2 \\sim O2: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C4 \\sim C3 \\sim N1: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08 within 2A
Mn1 \\sim N1: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
C1 \\sim O1 \\sim Mn1: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(O2) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C15B) = Uanis(C14B)
Uanis(C1) = Uanis(O1)
5. Rigid body (RIGU) restrains
 C4, C3, N1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Mn1, C2, O2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Mn1, N1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C15B, C14B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, O1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C13A, C12A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C15B)=Sof(H15B)=Sof(C14B)=Sof(H14B)=Sof(C13B)=Sof(H13B)=Sof(C12B)=
 Sof(H12B)=1-FVAR(1)
 Sof(C15A)=Sof(H15A)=Sof(C14A)=Sof(H14A)=Sof(C13A)=Sof(H13A)=Sof(C12A)=
 Sof(H12A)=FVAR(1)
 Fixed Sof: H31A(0.75) C20A(0.5) H20A(0.5) C19A(0.5) H19A(0.5) C23A(0.5)
 H23A(0.5) C22A(0.5) H22A(0.5) C23B(0.5) H23B(0.5) C20B(0.5) H20B(0.5)
 C19B(0.5) H19B(0.5) C22B(0.5) H22B(0.5) Br1(0.375) H4A(0.5) H4B(0.5) H4C(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C29(H29A,H29B), C5(H5A,H5B)
7.b Aromatic/amide H refined with riding coordinates:
 C39(H39), C37(H37), C40(H40), C36(H36), C15A(H15A), C20A(H20A), C14A(H14A),
 C19A(H19A), C13A(H13A), C12A(H12A), C23A(H23A), C22A(H22A), C23B(H23B),
 C20B(H20B), C19B(H19B), C22B(H22B), C15B(H15B), C14B(H14B), C13B(H13B),
 C12B(H12B)
7.c Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C31(H31A,H31B,H31C), C34(H34A,H34B,H34C), C7(H7A,H7B,
 H7C), C26(H26A,H26B,H26C), C10(H10A,H10B,H10C), C52(H52A,H52B,H52C), C4(H4A,
 H4B,H4C)
;
_shelx_res_checksum              65466
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'