Organofunctionalized borotungstate polyoxometalates as tunable photocatalysts for oxidative dimerization of amines.
Tsang, Nicole; Kibler, Alexander J.; Argent, Stephen P.; Lam, Hon Wai; Jones, Kieran D.; Newton, Graham N.; Chemical science 15 (2024) 14685–14691; doi:10.1039/d4sc03534h

data_1572319
_publ_section_title
;
 Organofunctionalized borotungstate polyoxometalates as tunable
 photocatalysts for oxidative dimerization of amines.
;
_journal_issue                   36
_journal_name_full               'Chemical science'
_journal_page_first              14685
_journal_page_last               14691
_journal_paper_doi               10.1039/d4sc03534h
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C18 H29 B K3 N6 O53 P2 W11, 4[H2O]'
_chemical_formula_sum            'C18 H37 B K3 N6 O57 P2 W11'
_chemical_formula_weight         3461.93
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-01-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-05-28 deposited with the CCDC.	2024-08-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 118.757(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.3035(4)
_cell_length_b                   23.9565(5)
_cell_length_c                   12.4053(4)
_cell_measurement_reflns_used    45639
_cell_measurement_temperature    100
_cell_measurement_theta_max      36.2580
_cell_measurement_theta_min      1.8060
_cell_volume                     3205.5(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.63a (Rigaku OD, 2023)'
_computing_data_collection       'GDA - generic data acquisition software'
_computing_data_reduction        'CrysAlisPro 1.171.43.63a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Photon counting pixel array'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.999
_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  \f      0.00 180.00   0.20    0.20   0.00   0.00   0.00    --   900
  2  \w   -145.00  25.00   0.20    0.20    --   30.00   0.00   0.00  850
  3  \w   -145.00  25.00   0.20    0.20    --   30.00   0.00 120.00  850
  4  \w   -145.00  25.00   0.20    0.20    --   30.00   0.00 240.00  850
;
_diffrn_measurement_device       'Fixed \c 3-circle diffractometer'
_diffrn_measurement_device_type  'Fluid Film Devices'
_diffrn_measurement_method       'shutterless scans'
_diffrn_measurement_specimen_support 'MiTeGen MicroMount'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0374566000
_diffrn_orient_matrix_UB_12      0.0125938000
_diffrn_orient_matrix_UB_13      -0.0555426000
_diffrn_orient_matrix_UB_21      -0.0510765000
_diffrn_orient_matrix_UB_22      -0.0128490000
_diffrn_orient_matrix_UB_23      -0.0021877000
_diffrn_orient_matrix_UB_31      -0.0081327000
_diffrn_orient_matrix_UB_32      0.0224380000
_diffrn_orient_matrix_UB_33      0.0303689000
_diffrn_radiation_monochromator  'Silicon 111'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.6889
_diffrn_reflns_av_R_equivalents  0.0929
_diffrn_reflns_av_unetI/netI     0.0595
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            41822
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        24.415
_diffrn_reflns_theta_max         25.499
_diffrn_reflns_theta_min         1.648
_diffrn_source                   synchrotron
_diffrn_source_details           'Allan et al. (2017)'
_diffrn_source_type              'Diamond Light Source Beamline I19-1'
_exptl_absorpt_coefficient_mu    18.283
_exptl_absorpt_correction_T_max  0.16674
_exptl_absorpt_correction_T_min  0.12894
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.63a (Rigaku Oxford Diffraction, 2023)
Spherical absorption correction
using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    3.587
_exptl_crystal_description       plate
_exptl_crystal_F_000             3098
_exptl_crystal_recrystallization_method
'Vapour diffusion nitromethane and tert-butyl methyl ether (antisolvent)'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.075
_exptl_crystal_size_min          0.075
_exptl_crystal_size_rad          0.075
_refine_diff_density_max         3.333
_refine_diff_density_min         -2.364
_refine_diff_density_rms         0.321
_refine_ls_abs_structure_details
;
 Flack x determined using 5237 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.074(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     850
_refine_ls_number_reflns         12893
_refine_ls_number_restraints     1897
_refine_ls_restrained_S_all      0.982
_refine_ls_R_factor_all          0.0510
_refine_ls_R_factor_gt           0.0498
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0368P)^2^+108.4183P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1167
_refine_ls_wR_factor_ref         0.1175
_reflns_Friedel_coverage         0.920
_reflns_Friedel_fraction_full    0.971
_reflns_Friedel_fraction_max     0.966
_reflns_number_gt                12500
_reflns_number_total             12893
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03534h2.cif
_cod_data_source_block           KPBW11
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_ambient_temperature' value '100 (2)' was changed
to '100(2)' -- the value was reformatted.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1572319--1572320.cif.
;
_cod_original_cell_volume        3205.49(19)
_cod_database_code               1572319
_nottingham_internal_coll_name   WKDJLF_D1
_nottingham_internal_coll_number 19249
_nottingham_internal_coll_client KJ/HWL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method 'fine \w scans'
_nottingham_internal_coll_frame_time 0.2
_nottingham_internal_coll_frame_width 0.01
_nottingham_internal_coll_user   pczspa
_nottingham_internal_coll_date   23/09/2022
_nottingham_internal_coll_location DLS
_nottingham_internal_coll_instrument i19-EH1
_nottingham_internal_process_date 16/11/2023
_nottingham_internal_process_user pczspa
_nottingham_internal_solution_date 16/11/2023
_nottingham_internal_solution_user pczspa
_nottingham_internal_refinement_date 19/12/2023
_nottingham_internal_refinement_user pczspa/pczkj1
_nottingham_internal_validation_date 19/12/2023
_nottingham_internal_validation_user pczspa
_nottingham_internal_archive_date 19/12/2023
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 B1 P2 W12 O40'
_shelx_estimated_absorpt_t_max   0.341
_shelx_estimated_absorpt_t_min   0.092
_olex2_refinement_description
;
1. Restrained distances
 O1C-H1C
 0.95 with sigma of 0.04
 P1A-C1A \\sim P1B-C1B
 with sigma of 0.02
 H1C-W2 \\sim H1C-W1
 with sigma of 0.04
 H1C-O2C \\sim H1C-O3C
 with sigma of 0.04
2. Restrained planarity
 O2E, N1E, C4E, O3E
 with sigma of 0.1
 O2F, N1F, C4F, O3F
 with sigma of 0.1
 O3J, C4J, N1J, O2J
 with sigma of 0.1
 N1G, O2G, O3G, C4G
 with sigma of 0.1
 N1H, O2H, O3H, C4H
 with sigma of 0.1
 N1I, O2I, O3I, C4I
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
Uanis(C4E) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(W1) \\sim Ueq, Uanis(C4H) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(O3E) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O19) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
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. Same fragment restrains
{C1A, C6A, C5A, C4A, C3A, C2A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C1A, C2A, C3A, C4A, C5A, C6A}
{N1E, O3E, O2E, C4E} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1E, O2E, O3E, C4E}
{N1E, O3E, O2E, C4E} sigma for 1-2: 0.02, 1-3: 0.04
{N1E, O2E, O3E, C4E} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1G, O2G, O3G, C4G}
{C1A, C2A, C3A, C4A, C5A, C6A} sigma for 1-2: 0.02, 1-3: 0.04
{C1A, C6A, C5A, C4A, C3A, C2A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C1B, C2B, C3B, C4B, C5B, C6B}
{N1E, O2E, O3E, C4E} sigma for 1-2: 0.02, 1-3: 0.04
{N1E, O3E, O2E, C4E} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1H, O2H, O3H, C4H}
{N1E, O3E, O2E, C4E} sigma for 1-2: 0.02, 1-3: 0.04
{N1E, O2E, O3E, C4E} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1I, O2I, O3I, C4I}
{N1E, O2E, O3E, C4E} sigma for 1-2: 0.02, 1-3: 0.04
{N1E, O3E, O2E, C4E} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1F, O2F, O3F, C4F}
{N1E, O2E, O3E, C4E} sigma for 1-2: 0.02, 1-3: 0.04
{N1E, O3E, O2E, C4E} sigma for 1-2: 0.02, 1-3: 0.04
as in
{N1J, O2J, O3J, C4J}
6.a Me refined with riding coordinates:
 C4E(H4EA,H4EB,H4EC), C4F(H4FA,H4FB,H4FC), C4G(H4GA,H4GB,H4GC), C4H(H4HA,H4HB,
 H4HC), C4I(H4IA,H4IB,H4IC), C4J(H4JA,H4JB,H4JC)
6.b Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A), C2B(H2B), C3B(H3B),
 C4B(H4B), C5B(H5B), C6B(H6B)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              2540
_shelx_hkl_checksum              72702
_shelx_fab_checksum              37473
_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 6.144
_oxdiff_exptl_absorpt_empirical_full_min 0.437