A bifunctional molecular catalyst built up of l-proline grafted polyoxometalate for one-pot three-component green synthesis of heterocycles
Dai, Guoyong; Li, Qi; Zang, Dejin; Wei, Yongge; Green Chemistry 25 (2023) 6263–6269; doi:10.1039/D3GC00951C

data_7246942
_publ_section_title
;
 A bifunctional molecular catalyst built up of l-proline grafted
 polyoxometalate for one-pot three-component green synthesis of
 heterocycles
;
_journal_issue                   16
_journal_name_full               'Green Chemistry'
_journal_page_first              6263
_journal_page_last               6269
_journal_paper_doi               10.1039/D3GC00951C
_journal_volume                  25
_journal_year                    2023
_chemical_absolute_configuration rmad
_chemical_formula_moiety
'C18 H32 Mn Mo6 N4 O26, C8 H24 Mo1.5 O8 S4, 7(C2 H6 O S)'
_chemical_formula_sum            'C46 H106 Mn Mo7.5 N4 O44 S14'
_chemical_formula_weight         2642.67
_chemical_name_systematic        L-Pro-Mn-Anderson
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-03-18
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-12-09 deposited with the CCDC.	2023-06-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   33.5555(4)
_cell_length_b                   30.4959(4)
_cell_length_c                   9.33799(9)
_cell_measurement_reflns_used    21640
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      75.8570
_cell_measurement_theta_min      4.1780
_cell_volume                     9555.61(19)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2137
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.991
_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    -60.00  31.00   1.00    4.82    --  -40.81  57.00  90.00   91
  2  \w   -115.00 -19.00   1.00    4.82    --  -40.81 -38.00 -60.00   96
  3  \w   -111.00 -27.00   1.00    4.82    --  -40.81 -38.00-150.00   84
  4  \w      6.00  60.00   1.00    4.82    --   40.81 -99.00-180.00   54
  5  \w     52.00  95.00   1.00    4.82    --   40.81-125.00 -90.00   43
  6  \w     28.00 109.00   1.00   19.29    --  110.27 -95.00  90.00   81
  7  \w     88.00 177.00   1.00   19.29    --  110.27  30.00-120.00   89
  8  \w     95.00 139.00   1.00   19.29    --  110.27 -77.00-180.00   44
  9  \w     91.00 122.00   1.00   19.29    --  110.27  30.00-150.00   31
 10  \w     49.00 103.00   1.00   19.29    --  110.27-125.00  30.00   54
 11  \w    151.00 177.00   1.00   19.29    --  110.27  30.00-150.00   26
 12  \w    100.00 167.00   1.00   19.29    --  110.27 125.00 150.00   67
 13  \w     55.00 143.00   1.00   19.29    --  110.27 -77.00 120.00   88
 14  \w     35.00  82.00   1.00   19.29    --  110.27 -30.00-150.00   47
 15  \w     41.00 109.00   1.00   19.29    --  110.27-125.00 -60.00   68
 16  \w    127.00 173.00   1.00   19.29    --  110.27  30.00 150.00   46
 17  \w     91.00 117.00   1.00   19.29    --  110.27-125.00  60.00   26
 18  \w     54.00 133.00   1.00   19.29    --  110.27 -30.00  30.00   79
 19  \w    120.00 177.00   1.00   19.29    --  110.27  77.00  90.00   57
 20  \w     56.00  82.00   1.00   19.29    --  110.27 -77.00-180.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0158147000
_diffrn_orient_matrix_UB_12      -0.0472700000
_diffrn_orient_matrix_UB_13      -0.0124889000
_diffrn_orient_matrix_UB_21      0.0413632000
_diffrn_orient_matrix_UB_22      0.0177583000
_diffrn_orient_matrix_UB_23      -0.0418123000
_diffrn_orient_matrix_UB_31      0.0121281000
_diffrn_orient_matrix_UB_32      0.0009674000
_diffrn_orient_matrix_UB_33      0.1591299000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0598
_diffrn_reflns_av_unetI/netI     0.0594
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       42
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            69366
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.393
_diffrn_reflns_theta_min         3.917
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.431
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65022
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_density_diffrn    1.837
_exptl_crystal_description       cylinder
_exptl_crystal_F_000             5304
_exptl_crystal_size_length       0.200
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_exptl_crystal_size_rad          0.030
_platon_squeeze_details
;
;
_refine_diff_density_max         1.582
_refine_diff_density_min         -1.397
_refine_diff_density_rms         0.135
_refine_ls_abs_structure_details
;
 Flack x determined using 7044 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.020(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1040
_refine_ls_number_reflns         19625
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0533
_refine_ls_R_factor_gt           0.0482
_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^)+(0.0504P)^2^+30.0886P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1165
_refine_ls_wR_factor_ref         0.1195
_reflns_Friedel_coverage         0.798
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.964
_reflns_number_gt                17924
_reflns_number_total             19625
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3gc00951c2.cif
_cod_data_source_block           exp_3927
_cod_depositor_comments
'Adding full bibliography for 7246941--7246942.cif.'
_cod_original_cell_volume        9555.6(2)
_cod_original_formula_sum        'C46 H106 Mn Mo7.50 N4 O44 S14'
_cod_database_code               7246942
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Mn Mo C N O'
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     64.99
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 S7B-O36B \\sim S7A-O36A
 with sigma of 0.02
 S6A-O35A \\sim S6B-O35B
 with sigma of 0.02
3. Rigid bond restraints
 C31, C32, O36B, S7B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C31, C32, O36A, S7A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C29, C30, O35A, S6A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C29, C30, O35B, S6B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(O36B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O35B) \\sim Ueq, Uanis(O35A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(S7A) = Uanis(S7B)
5. Others
 Fixed Sof: H19D(0.5) H19E(0.5) H19F(0.5) H19A(0.5) H19B(0.5) H19C(0.5)
 H20D(0.5) H20E(0.5) H20F(0.5) H20A(0.5) H20B(0.5) H20C(0.5) O27A(0.5)
 O27B(0.5) O30A(0.5) O30B(0.5) S1A(0.5) S1B(0.5) H29D(0.5) H29E(0.5) H29F(0.5)
 H29A(0.5) H29B(0.5) H29C(0.5) H30D(0.5) H30E(0.5) H30F(0.5) H30A(0.5)
 H30B(0.5) H30C(0.5) O35A(0.5) O35B(0.5) S6A(0.5) S6B(0.5) H31A(0.75)
 H31B(0.75) H31C(0.75) H31D(0.25) H31E(0.25) H31F(0.25) H32A(0.75) H32B(0.75)
 H32C(0.75) H32D(0.25) H32E(0.25) H32F(0.25) O36A(0.75) O36B(0.25) S7A(0.75)
 S7B(0.25) H33A(0.5) H33B(0.5) H33C(0.5) H33D(0.5) H33E(0.5) H33F(0.5)
 C34A(0.5) H34A(0.5) H34B(0.5) H34C(0.5) C34B(0.5) H34D(0.5) H34E(0.5)
 H34F(0.5) S8A(0.5) S8B(0.5)
6.a Ternary CH refined with riding coordinates:
 C6(H6), C15(H15)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B),
 C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C16(H16A,H16B), C17(H17A,H17B),
  C18(H18A,H18B), N2(H2C,H2D), N4(H4A,H4B)
6.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N3(H3)
6.d Idealised Me refined as rotating group:
 C19(H19D,H19E,H19F), C19(H19A,H19B,H19C), C20(H20D,H20E,H20F), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,
 H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C),
 C28(H28A,H28B,H28C), C29(H29D,H29E,H29F), C29(H29A,H29B,H29C), C30(H30D,H30E,
 H30F), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C31(H31D,H31E,H31F), C32(H32A,
 H32B,H32C), C32(H32D,H32E,H32F), C33(H33A,H33B,H33C), C33(H33D,H33E,H33F),
 C34A(H34A,H34B,H34C), C34B(H34D,H34E,H34F), C35(H35A,H35B,H35C), C36(H36A,H36B,
 H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,
 H40B,H40C)
;
_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 1.503
_oxdiff_exptl_absorpt_empirical_full_min 0.662