Imparting structural robustness of Metal-Organic Cages based on oxo-dimolybdenum clusters
Delaporte , Solène; Abánades Lázaro, Isabel; Lopez-Cabrelles, Javier; Mazarakioti, Eleni C.; Chebourou, Sarah; Vitórica-Yrezábal, Iñigo J.; Giménez-Marqués, Mónica; Minguez Espallargas, Guillermo; Dalton Transactions  (2023) –; doi:10.1039/D3DT02482B

data_7713777
_publ_section_title
;
 Imparting structural robustness of Metal-Organic Cages based on
 oxo-dimolybdenum clusters
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02482B
_journal_year                    2023
_chemical_formula_moiety
'C114 H78 Mo12 N12 O60, 15.038(C3 H7 N O), 6(C2 H8 N), 0.962(C3 H6 N O)'
_chemical_formula_sum            'C174 H237.05 Mo12 N34 O76'
_chemical_formula_weight         5172.29
_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             2022-11-25
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-04-21 deposited with the CCDC.	2023-08-22 downloaded from the CCDC.
;
_cell_angle_alpha                109.122(5)
_cell_angle_beta                 104.775(5)
_cell_angle_gamma                109.834(6)
_cell_formula_units_Z            1
_cell_length_a                   19.2467(13)
_cell_length_b                   19.8669(13)
_cell_length_c                   19.9079(11)
_cell_measurement_reflns_used    4428
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      21.6290
_cell_measurement_theta_min      2.0260
_cell_volume                     6164.7(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_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  \w    -67.00 -22.00   1.00   50.00    --    5.00 -22.00 173.00   45
  2  \w    -18.00  68.00   1.00   50.00    --    5.00 -22.00 173.00   86
  3  \w    -93.00  24.00   1.00   50.00    --   -8.00 -57.00  60.00  117
  4  \w    -83.00  15.00   1.00   50.00    --   -8.00 -76.00-150.00   98
  5  \w    -20.00   6.00   1.00   50.00    --   -8.00  57.00 150.00   26
  6  \w     28.00  54.00   1.00   50.00    --   -8.00  57.00 150.00   26
  7  \w    -97.00  -7.00   1.00   50.00    --   -8.00 -57.00 -30.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0240174000
_diffrn_orient_matrix_UB_12      0.0341572000
_diffrn_orient_matrix_UB_13      -0.0028484000
_diffrn_orient_matrix_UB_21      0.0232314000
_diffrn_orient_matrix_UB_22      -0.0188307000
_diffrn_orient_matrix_UB_23      -0.0116361000
_diffrn_orient_matrix_UB_31      -0.0270574000
_diffrn_orient_matrix_UB_32      -0.0172008000
_diffrn_orient_matrix_UB_33      -0.0396138000
_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  0.1532
_diffrn_reflns_av_unetI/netI     0.1659
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            82214
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         1.775
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Mo) X-ray DW Source'
_exptl_absorpt_coefficient_mu    0.670
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48696
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.393
_exptl_crystal_description       needle
_exptl_crystal_F_000             2631
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.431
_refine_diff_density_min         -0.878
_refine_diff_density_rms         0.140
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.970
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1150
_refine_ls_number_reflns         22535
_refine_ls_number_restraints     63
_refine_ls_restrained_S_all      0.971
_refine_ls_R_factor_all          0.1858
_refine_ls_R_factor_gt           0.0822
_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^)+(0.1410P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2081
_refine_ls_wR_factor_ref         0.2613
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10501
_reflns_number_total             22535
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02482b2.cif
_cod_data_source_block           rivy31
_cod_original_cell_volume        6164.7(7)
_cod_database_code               7713777
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.987
_shelx_estimated_absorpt_t_min   0.967
_diffrn_oxdiff_ac4_digest_frames
;
01b71867f3bb46232163bb38750f9e88c50048853fa
;
_olex2_refinement_description
;
1. Restrained distances
 N18S-C19S \\sim N18S-C20S
 with sigma of 0.02
 N33S-C35S \\sim N33S-C34S
 with sigma of 0.02
 N13S-C14S \\sim N13S-C15S
 with sigma of 0.02
 N23S-C25S \\sim N23S-C24S
 with sigma of 0.02
 N28S-C30S \\sim N28S-C29S
 with sigma of 0.02
 N3S-C5S \\sim N3S-C4S
 with sigma of 0.02
 N47S-C48S \\sim N47S-C49S
 with sigma of 0.02
 N38S-C40S \\sim N38S-C39S
 with sigma of 0.02
 N8S-C10S \\sim N8S-C9S
 with sigma of 0.02
2. Restrained planarity
 C32S, O31S, N33S, C35S, C34S
 with sigma of 0.1
 C27S, O26S, N28S, C30S, C29S
 with sigma of 0.1
 C12S, O11S, N13S, C14S, C15S
 with sigma of 0.1
 C17S, O16S, N18S, C19S, C20S
 with sigma of 0.1
 C22S, O21S, N23S, C25S, C24S
 with sigma of 0.1
 C2S, O1S, N3S, C5S, C4S
 with sigma of 0.1
 C46S, O45S, N47S, C48S, C49S
 with sigma of 0.1
 C37S, O36S, N38S, C40S, C39S
 with sigma of 0.1
 C7S, O6S, N8S, C10S, C9S
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
C12S \\sim O11S \\sim N13S \\sim C14S \\sim C15S: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C32S \\sim O31S \\sim N33S \\sim C35S \\sim C34S: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C2S \\sim O1S \\sim N3S \\sim C5S \\sim C4S: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C19S \\sim C20S \\sim N18S \\sim C17S \\sim O16S: within 2A with sigma of 0.02
and sigma for terminal atoms of 0.04 within 2A
C24S \\sim C22S \\sim O21S \\sim N23S \\sim C25S: within 2A with sigma of 0.02
and sigma for terminal atoms of 0.04 within 2A
C17S \\sim O16S \\sim N18S \\sim C19S \\sim C20S: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C22S \\sim O21S \\sim N23S \\sim C25S \\sim C24S: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C27S \\sim O26S \\sim N28S \\sim C30S \\sim C29S: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C46S \\sim O45S \\sim N47S \\sim C48S \\sim C49S: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C37S \\sim O36S \\sim N38S \\sim C40S \\sim C39S: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C7S \\sim O6S \\sim N8S \\sim C10S \\sim C9S: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C32S, O31S, N33S, C35S, C34S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C12S, O11S, N13S, C14S, C15S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C27S, O26S, N28S, C30S, C29S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C17S, O16S, N18S, C19S, C20S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C22S, O21S, N23S, C25S, C24S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2S, O1S, N3S, C5S, C4S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C46S, O45S, N47S, C48S, C49S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C37S, O36S, N38S, C40S, C39S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7S, O6S, N8S, C10S, C9S
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C7S)=Sof(H7S)=Sof(O6S)=Sof(N8S)=Sof(C10S)=Sof(H10A)=Sof(H10B)=Sof(H10C)=
 Sof(C9S)=Sof(H9SA)=Sof(H9SB)=Sof(H9SC)=1-FVAR(1)
 Sof(C12S)=Sof(H12S)=Sof(O11S)=Sof(N13S)=Sof(C14S)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=Sof(C15S)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(1)
 Sof(C45S)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(O41S)=Sof(C64)=Sof(H64A)=
 Sof(H64B)=Sof(H64C)=Sof(C42S)=Sof(H42S)=Sof(N43S)=1-FVAR(2)
 Sof(C37S)=Sof(O36S)=Sof(N38S)=Sof(C40S)=Sof(H40A)=Sof(H40B)=Sof(H40C)=
 Sof(C39S)=Sof(H39A)=Sof(H39B)=Sof(H39C)=FVAR(2)
 Sof(C17S)=Sof(H17S)=Sof(O16S)=Sof(N18S)=Sof(C19S)=Sof(H19A)=Sof(H19B)=
 Sof(H19C)=Sof(C20S)=Sof(H20A)=Sof(H20B)=Sof(H20C)=1-FVAR(3)
 Sof(C22S)=Sof(H22S)=Sof(O21S)=Sof(N23S)=Sof(C25S)=Sof(H25A)=Sof(H25B)=
 Sof(H25C)=Sof(C24S)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(3)
6.a Riding coordinates:
 C44S(H44A,H44B,H44C)
6.b Free rotating group:
 C17S(O16S,N18S,C19S,C20S), C22S(O21S,N23S,C25S,C24S), C27S(O26S,N28S,C30S,
 C29S), C2S(O1S,N3S,C5S,C4S), C32S(O31S,N33S,C35S,C34S), C46S(O45S,N47S,C48S,
 C49S), C37S(O36S,N38S,C40S,C39S), C7S(O6S,N8S,C10S,C9S), C12S(O11S,N13S,C14S,
 C15S)
6.c Secondary CH2 refined with riding coordinates:
 N9(H9A,H9B), N8(H8A,H8B), N7(H7A,H7B)
6.d Me refined with riding coordinates:
 C63(H63A,H63B,H63C), C58(H58A,H58B,H58C), C43S(H43A,H43B,H43C), C45S(H45A,
 H45B,H45C), C62(H62A,H62B,H62C), C59(H59A,H59B,H59C), C61(H61A,H61B,H61C),
 C60(H60A,H60B,H60C), C64(H64A,H64B,H64C), C19S(H19A,H19B,H19C), C20S(H20A,H20B,
 H20C), C25S(H25A,H25B,H25C), C24S(H24A,H24B,H24C), C30S(H30A,H30B,H30C),
 C29S(H29A,H29B,H29C), C5S(H5SA,H5SB,H5SC), C4S(H4SA,H4SB,H4SC), C35S(H35A,H35B,
 H35C), C34S(H34A,H34B,H34C), C48S(H48A,H48B,H48C), C49S(H49A,H49B,H49C),
 C40S(H40A,H40B,H40C), C39S(H39A,H39B,H39C), C10S(H10A,H10B,H10C), C9S(H9SA,
 H9SB,H9SC), C14S(H14A,H14B,H14C), C15S(H15A,H15B,H15C)
6.e Aromatic/amide H refined with riding coordinates:
 C32(H32), C55(H55), C13(H13), C15(H15), C51(H51), C36(H36), C17(H17),
 C34(H34), C53(H53), C45(H45), C46(H46), C39(H39), C42(H42), C48(H48), C20(H20),
  C6(H6), C24(H24), C44(H44), C23(H23), C40(H40), C22(H22), C4(H4), C27(H27),
 C7(H7), C5(H5), C43(H43), C47(H47), C28(H28), C3(H3), C21(H21), C1(H1),
 C41(H41), C8(H8), C29(H29), C41S(H41S), C10(H10), C2(H2), C25(H25), C9(H9),
 C26(H26), C42S(H42S), C17S(H17S), C22S(H22S), C27S(H27S), C2S(H2S), C32S(H32S),
  C46S(H46S), C7S(H7S), C12S(H12S)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 77 electrons were 
found in a volume of 353\%A^3^ in 4 voids per unit cell. 
This is consistent with the presence of 
1.5[C3H7NO] per Formula Unit 
which account for 60 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              77925
_shelx_fab_checksum              10435
_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 1.803
_oxdiff_exptl_absorpt_empirical_full_min 0.570