A series of rare-earth phosphine-oxygen complexes containing [PW12O40]3− with highly efficient photocatalytic degradation of MB
Li, Ying-Yu; Qiu, Qi-Ming; Fan, Si-Jie; Xu, Jian-Jie; Mou, Wen-Long; Hou, Chuan-Bing; Liu, Min; Yang, Yu-Ping; Dai, Li-Xiong; Han, Hong-Liang; Jin, Qiong-Hua; CrystEngComm 26 (2024) 5809–5819; doi:10.1039/D4CE00851K

data_7249345
_publ_section_title
;
 A series of rare-earth phosphine-oxygen complexes containing
 [PW12O40]3&#x2212; with highly efficient photocatalytic degradation of MB
;
_journal_issue                   40
_journal_name_full               CrystEngComm
_journal_page_first              5809
_journal_page_last               5819
_journal_paper_doi               10.1039/D4CE00851K
_journal_volume                  26
_journal_year                    2024
_chemical_formula_moiety         '2(O20 P0.5 W6), C42 H98 O20 P6 Tm, 2(C2 H3 N)'
_chemical_formula_sum            'C46 H104 N2 O60 P7 Tm W12'
_chemical_formula_weight         4237.23
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-02-26
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2023-03-10 deposited with the CCDC.	2024-09-12 downloaded from the CCDC.
;
_cell_angle_alpha                104.785(2)
_cell_angle_beta                 94.446(2)
_cell_angle_gamma                116.285(2)
_cell_formula_units_Z            2
_cell_length_a                   15.5807(3)
_cell_length_b                   16.9400(3)
_cell_length_c                   21.7710(4)
_cell_measurement_reflns_used    23014
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      31.1440
_cell_measurement_theta_min      2.3760
_cell_volume                     4859.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -23.00  40.00   0.70    2.00    --    2.03  91.00-108.00   90
  2  \w    -32.00  10.70   0.70    2.00    --   -5.15  91.00-108.00   61
  3  \w    -65.00   5.00   0.70    2.00    --    2.03 -38.00  60.00  100
  4  \w    -73.00  -3.00   0.70    2.00    --   -5.15 -19.00 120.00  100
  5  \w    -36.00  28.40   0.70    2.00    --    2.03 -91.00 137.00   92
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0022887000
_diffrn_orient_matrix_UB_12      -0.0076123000
_diffrn_orient_matrix_UB_13      0.0305324000
_diffrn_orient_matrix_UB_21      0.0519240000
_diffrn_orient_matrix_UB_22      0.0210833000
_diffrn_orient_matrix_UB_23      0.0082197000
_diffrn_orient_matrix_UB_31      0.0027464000
_diffrn_orient_matrix_UB_32      0.0439778000
_diffrn_orient_matrix_UB_33      0.0139006000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0505
_diffrn_reflns_av_unetI/netI     0.0589
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            46599
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.030
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    15.250
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.17003
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (Rigaku Oxford Diffraction, 2021)
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    2.896
_exptl_crystal_description       block
_exptl_crystal_F_000             3872
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         4.336
_refine_diff_density_min         -4.080
_refine_diff_density_rms         0.311
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1235
_refine_ls_number_reflns         17005
_refine_ls_number_restraints     1188
_refine_ls_restrained_S_all      1.140
_refine_ls_R_factor_all          0.0696
_refine_ls_R_factor_gt           0.0580
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+242.0884P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1237
_refine_ls_wR_factor_ref         0.1280
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14503
_reflns_number_total             17005
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce00851k21.cif
_cod_data_source_block           exp_1651_auto
_cod_depositor_comments
'Adding full bibliography for 7249339--7249349.cif.'
_cod_original_cell_volume        4859.65(18)
_cod_database_code               7249345
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'Tm Cl O C W P'
_shelx_estimated_absorpt_t_max   0.311
_shelx_estimated_absorpt_t_min   0.208
_reflns_odcompleteness_completeness 99.07
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, H26 of C26, H24 of C24, H40 of C40, H39 of C39, H10 of
  C10, H13 of C13, H8 of C8, H7 of C7, H14 of C14, H16 of C16, H3 of C3, H17 of
  C17
 At 1.5 times of:
  All C(H,H,H) groups, H51 of C51, All O(H,H) groups
2. Uiso/Uaniso restraints and constraints
P8 \\sim O44 \\sim C7 \\sim C1 \\sim C34: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C42 \\sim C40 \\sim C25 \\sim O65 \\sim P7: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
O40 \\sim C39 \\sim C12 \\sim C41: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C5 \\sim C13 \\sim C45 \\sim O10 \\sim P3: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
P5 \\sim O39 \\sim C16 \\sim C21 \\sim C38: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C2 \\sim C28: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
P7 \\sim O25 \\sim C10 \\sim C15 \\sim C37: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C43 \\sim C44 \\sim N3: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O11 \\sim W2 \\sim O6 \\sim O13 \\sim O15 \\sim O33 \\sim O36 \\sim W5 \\sim
W11 \\sim O17 \\sim O28 \\sim O30 \\sim O60 \\sim O37 \\sim W4 \\sim W9 \\sim
W10 \\sim O3 \\sim O7 \\sim O8 \\sim O16 \\sim O18 \\sim O12 \\sim O53 \\sim
O55 \\sim O59 \\sim O57 \\sim P4 \\sim O9: within 3.8A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 3.8A
C20 \\sim P2 \\sim C32 \\sim P3: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C46 \\sim C19: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
W12 \\sim O49: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
W7 \\sim O47 \\sim W8 \\sim O67 \\sim W1: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
O50 \\sim W8 \\sim W6 \\sim O22 \\sim W3 \\sim O31: within 2A with sigma of
0.001 and sigma for terminal atoms of 0.002 within 2A
W3 \\sim O45 \\sim W7 \\sim O48 \\sim W12: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
W6 \\sim O23 \\sim W1: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
W1 \\sim O5 \\sim W12: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
W7 \\sim O41 \\sim W12: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
W1 \\sim O62: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
W1 \\sim O23 \\sim O67 \\sim O5 \\sim O31: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
W6 \\sim O66 \\sim W7: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
Uanis(O19) = Uanis(O2) = Uanis(P1) = Uanis(O1) = Uanis(O4)
3. Others
 Fixed Sof: W5(0.5) W9(0.5) W10(0.5) W11(0.5) O1(0.5) O2(0.5) O3(0.5) O4(0.5)
 O7(0.5) O9(0.5) O12(0.5) O19(0.5) W5A(0.5) W11A(0.5) W9A(0.5) W10A(0.5)
4.a Rotating group:
 O54(H54A,H54B), O63(H63A,H63B)
4.b Ternary CH refined with riding coordinates:
 C3(H3), C7(H7), C8(H8), C13(H13), C14(H14), C16(H16), C17(H17), C24(H24),
 C26(H26), C39(H39), C40(H40)
4.c Secondary CH2 refined with riding coordinates:
 C32(H32A,H32B), C46(H46A,H46B), C19(H19A,H19B), C20(H20A,H20B), C27(H27A,
 H27B), C33(H33A,H33B)
4.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C9(H9A,
 H9B,H9C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C15(H15A,H15B,H15C),
 C18(H18A,H18B,H18C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C25(H25A,H25B,
 H25C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C45(H45A,
 H45B,H45C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C),
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C41(H41A,H41B,H41C), C42(H42A,H42B,
 H42C), C44(H44A,H44B,H44C), C28(H28A,H28B,H28C)
4.e Idealised tetrahedral OH refined as rotating group:
 C51(H51)
;
_shelx_res_checksum              39548
_shelx_hkl_checksum              13034
_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 4.097
_oxdiff_exptl_absorpt_empirical_full_min 0.506