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_1572320
_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_formula_moiety
'0.99(C12 H11 As2 B O41 W11), 0.01(W12 O40 B), 3(K), 7(C H3 N O2), H2O'
_chemical_formula_sum            'C18.88 H33.89 As1.98 B K3 N7 O55.99 W11.01'
_chemical_formula_weight         3555.46
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-12-15
_audit_creation_method
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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                 97.73
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.186
_cell_length_b                   23.16170(10)
_cell_length_c                   23.13750(10)
_cell_measurement_reflns_used    121320
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      35.029862751295575
_cell_measurement_theta_min      0.8511874734767082
_cell_volume                     6471.18(4)
_computing_data_collection       'GDA - generic data acquisition software'
_computing_data_reduction
;
aimless (Evans, P. R. and Murshudov, G. N., 2013)
ccp4 (Winn, M. D. et al., 2011)
DIALS 3.11.1-g247d2660a-release (Winter, G. et al., 2018)
pointless (Evans, P., 2006)
XIA2 3.11.0 (Winter, G., 2010)
;
_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_type            'Dectris PILATUS 2M'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.955
_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_radiation_monochromator  'Silicon 111'
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.6889
_diffrn_reflns_av_R_equivalents  0.0685
_diffrn_reflns_av_unetI/netI     0.0425
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            282940
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        24.415
_diffrn_reflns_theta_max         36.114
_diffrn_reflns_theta_min         1.211
_diffrn_source                   Synchrotron
_diffrn_source_details           'Allan et al. (2017)'
_diffrn_source_type              'Diamond Light Source Beamline I19-1'
_exptl_absorpt_coefficient_mu    18.996
_exptl_absorpt_correction_T_max  1.0
_exptl_absorpt_correction_T_min  0.9350628092347374
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
;
CCP4 8.0.003: AIMLESS, version 0.7.9 : 10/06/22
Scaling & analysis of unmerged intensities, absorption correction using spherical harmonics
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    3.649
_exptl_crystal_description       block
_exptl_crystal_F_000             6345
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         3.774
_refine_diff_density_min         -2.825
_refine_diff_density_rms         0.320
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     957
_refine_ls_number_reflns         32415
_refine_ls_number_restraints     933
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0443
_refine_ls_R_factor_gt           0.0354
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0045P)^2^+72.4676P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0746
_refine_ls_wR_factor_ref         0.0768
_reflns_Friedel_coverage         0.000
_reflns_number_gt                27629
_reflns_number_total             32415
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03534h2.cif
_cod_data_source_block           KAsBW11
_cod_depositor_comments
'Adding full bibliography for 1572319--1572320.cif.'
_cod_original_cell_volume        6471.15(4)
_cod_database_code               1572320
_nottingham_internal_coll_name   WKDJLE_1
_nottingham_internal_coll_number 19213
_nottingham_internal_coll_client KJ/HWL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method 0.01
_nottingham_internal_coll_frame_time 'fine \w scans'
_nottingham_internal_coll_frame_width 0.2
_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 23/09/2022
_nottingham_internal_process_user pczspa
_nottingham_internal_solution_date 16/11/2023
_nottingham_internal_solution_user pczspa/pczkj1
_nottingham_internal_refinement_date 15/12/2023
_nottingham_internal_refinement_user pczpsa/pczkj1
_nottingham_internal_validation_date 15/12/2023
_nottingham_internal_validation_user pczpsa
_nottingham_internal_archive_date 15/12/2023
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.600
_shelx_estimated_absorpt_t_min   0.191
_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, All K(H) groups
2. Shared sites
{C1X, C1A}
3. Restrained distances
 O1C-H1C
 0.95 with sigma of 0.02
 As1A-C1A \\sim As1A-C1X
 with sigma of 0.02
 C1A-C2A \\sim C1X-C2X
 with sigma of 0.02
 C1A-C6A \\sim C1X-C6X
 with sigma of 0.02
 C1A-C3A \\sim C1X-C3X
 with sigma of 0.04
 C1A-C5A \\sim C1X-C5X
 with sigma of 0.04
 C2A-C3A \\sim C2X-C3X
 with sigma of 0.02
 C3A-C4A \\sim C3X-C4X
 with sigma of 0.02
 C4A-C5A \\sim C4X-C5X
 with sigma of 0.02
 C5A-C6A \\sim C5X-C6X
 with sigma of 0.02
 As1A-C2A \\sim As1A-C2X
 with sigma of 0.04
 As1A-C6A \\sim As1A-C6X
 with sigma of 0.04
 C2A-C4A \\sim C2X-C4X
 with sigma of 0.04
 C2A-C6A \\sim C2X-C6X
 with sigma of 0.04
 C3A-C5A \\sim C3X-C5X
 with sigma of 0.04
 C4A-C6A \\sim C4X-C6X
 with sigma of 0.04
4. Restrained planarity
 C1X, C2X, C3X, C4X, C5X, C6X
 with sigma of 0.1
 C1A, C2A, C3A, C4A, C5A, C6A
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
O3G \\sim O4H \\sim O3F \\sim C1J \\sim O3E \\sim O4I \\sim N2J \\sim C1K \\sim
O3I \\sim C1F \\sim C1E \\sim C1G \\sim N2I \\sim O3J \\sim O3H \\sim C1H \\sim
N2E \\sim O4J \\sim O4E \\sim O3K \\sim N2F \\sim N2G \\sim O4F \\sim C1I \\sim
N2K \\sim O4K \\sim O4G \\sim N2H: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A \\sim C1B \\sim C2B \\sim
C3B \\sim C4B \\sim C5B \\sim C6B \\sim C1E \\sim C1F \\sim C1G \\sim C1H \\sim
C1I \\sim C1J \\sim C1K \\sim C1X \\sim C2X \\sim C3X \\sim C4X \\sim C5X \\sim
C6X \\sim As1A \\sim As1B: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A \\sim C1B \\sim C2B \\sim
C3B \\sim C4B \\sim C5B \\sim C6B: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
K1B \\sim K1A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
K3 \\sim K3A: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
Uanis(N2G) \\sim Ueq, Uanis(O3G) \\sim Ueq, Uanis(O4G) \\sim Ueq, Uanis(C1G)
\\sim Ueq, Uanis(O4H) \\sim Ueq, Uanis(N2H) \\sim Ueq, Uanis(O3H) \\sim Ueq,
Uanis(C1H) \\sim Ueq, Uanis(O3F) \\sim Ueq, Uanis(N2F) \\sim Ueq, Uanis(C1F)
\\sim Ueq, Uanis(O4F) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C1X) = Uanis(C1A)
Uanis(K3A) = Uanis(K3)
6. Rigid body (RIGU) restrains
 C1A, C2A, C3A, C4A, C5A, C6A, C1B, C2B, C3B, C4B, C5B, C6B, C1E, C1F, C1G,
 C1H, C1I, C1J, C1K, C1X, C2X, C3X, C4X, C5X, C6X, As1A, As1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3G, O4H, O3F, C1J, O3E, O4I, N2J, C1K, O3I, C1F, C1E, C1G, N2I, O3J, O3H,
 C1H, N2E, O4J, O4E, O3K, N2F, N2G, O4F, C1I, N2K, O4K, O4G, N2H
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C2A, C3A, C4A, C5A, C6A, C1B, C2B, C3B, C4B, C5B, C6B
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
7. Same fragment restrains
{C1E, N2E, O4E, O3E} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C1E, N2E, O3E, O4E}
{C1E, N2E, O4E, O3E} sigma for 1-2: 0.02, 1-3: 0.04
{C1E, N2E, O3E, O4E} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C1J, N2J, O3J, O4J}
{C1E, N2E, O4E, O3E} sigma for 1-2: 0.02, 1-3: 0.04
{C1E, N2E, O3E, O4E} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C1I, N2I, O3I, O4I}
{C1E, N2E, O3E, O4E} sigma for 1-2: 0.02, 1-3: 0.04
{C1E, N2E, O4E, O3E} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C1F, N2F, O3F, O4F}
{C1E, N2E, O3E, O4E} sigma for 1-2: 0.02, 1-3: 0.04
{C1E, N2E, O4E, O3E} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C1H, N2H, O3H, O4H}
{C1E, N2E, O3E, O4E} sigma for 1-2: 0.02, 1-3: 0.04
{C1E, N2E, O4E, O3E} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C1G, N2G, O3G, O4G}
{C1E, N2E, O4E, O3E} sigma for 1-2: 0.02, 1-3: 0.04
{C1E, N2E, O3E, O4E} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C1K, N2K, O3K, O4K}
8. Others
 Sof(W12)=1-FVAR(1)
 Sof(As1A)=Sof(As1B)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(O5)=Sof(O1A)=Sof(O1B)=
 Sof(C1B)=Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(H4B)=Sof(C5B)=
 Sof(H5B)=Sof(C6B)=Sof(H6B)=Sof(H1C)=FVAR(1)
 Sof(K1B)=1-FVAR(2)
 Sof(K1A)=FVAR(2)
 Sof(K3A)=1-FVAR(3)
 Sof(K3)=FVAR(3)
 Sof(C1X)=Sof(C2X)=Sof(H2X)=Sof(C3X)=Sof(H3X)=Sof(C4X)=Sof(H4X)=Sof(C5X)=
 Sof(H5X)=Sof(C6X)=Sof(H6X)=1-FVAR(4)
 Sof(C1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=
 Sof(H5A)=Sof(C6A)=Sof(H6A)=FVAR(4)
 Fixed Uiso: O1W(0.08)
9.a 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), C2X(H2X), C3X(H3X), C4X(H4X), C5X(H5X), C6X(H6X)
9.b Idealised Me refined as rotating group:
 C1E(H1EA,H1EB,H1EC), C1F(H1FA,H1FB,H1FC), C1G(H1GA,H1GB,H1GC), C1H(H1HA,H1HB,
 H1HC), C1I(H1IA,H1IB,H1IC), C1J(H1JA,H1JB,H1JC), C1K(H1KA,H1KB,H1KC)
;
_shelx_res_checksum              25813
_shelx_hkl_checksum              22588
_olex2_submission_special_instructions 'No special instructions were received'