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_7713773
_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
'C126 H102 Mo12 N12 O60, 6(C2 H8 N), 2(C3 H7 N O)'
_chemical_formula_sum            'C144 H164 Mo12 N20 O62'
_chemical_formula_weight         4318.22
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_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                90
_cell_angle_beta                 101.313(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   21.5269(11)
_cell_length_b                   14.7675(7)
_cell_length_c                   32.448(2)
_cell_measurement_reflns_used    12325
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      17.8310
_cell_measurement_theta_min      3.0060
_cell_volume                     10114.7(10)
_computing_cell_refinement       'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.109a (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  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.0267
_diffrn_detector_type            Sapphire3
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -85.00   6.00   1.00   20.00    --  -16.06 -57.00 -90.00   91
  2  \w    -85.00   6.00   1.00   20.00    --  -16.06 -57.00  90.00   91
  3  \w    -85.00   6.00   1.00   20.00    --  -16.06 -57.00-180.00   91
  4  \w    -48.00  42.00   1.00   20.00    --  -16.06  77.00  60.00   90
  5  \w    -48.00  42.00   1.00   20.00    --  -16.06  77.00 150.00   90
  6  \w    -85.00   6.00   1.00   20.00    --  -16.06 -57.00   0.00   91
  7  \w    -48.00  42.00   1.00   20.00    --  -16.06  77.00 -30.00   90
  8  \w    -42.00  49.00   1.00   20.00    --   16.99 -77.00-120.00   91
  9  \w    -43.00  54.00   1.00   20.00    --  -16.06  38.00 -30.00   97
 10  \w    -78.00  -9.00   1.00   20.00    --  -16.06 131.00  70.76   69
 11  \w    -15.00  60.00   1.00   20.00    --   16.99 -99.00 -90.00   75
 12  \w    -15.00  42.00   1.00   20.00    --   16.99  77.00 -30.00   57
 13  \w    -15.00  42.00   1.00   20.00    --   16.99  77.00-180.00   57
 14  \w      7.00  76.00   1.00   20.00    --   16.99-126.00  -1.32   69
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Single source at offset/far, Sapphire3'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0047456000
_diffrn_orient_matrix_UB_12      -0.0038822000
_diffrn_orient_matrix_UB_13      -0.0209379000
_diffrn_orient_matrix_UB_21      -0.0025888000
_diffrn_orient_matrix_UB_22      0.0476801000
_diffrn_orient_matrix_UB_23      -0.0023578000
_diffrn_orient_matrix_UB_31      0.0331738000
_diffrn_orient_matrix_UB_32      0.0042968000
_diffrn_orient_matrix_UB_33      0.0072939000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.0807
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_number            10579
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        20.815
_diffrn_reflns_theta_max         20.815
_diffrn_reflns_theta_min         2.804
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.794
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79815
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.109a (Rigaku Oxford Diffraction, 2021)
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    1.418
_exptl_crystal_description       needle
_exptl_crystal_F_000             4336
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.297
_refine_diff_density_min         -1.178
_refine_diff_density_rms         0.213
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1217
_refine_ls_number_reflns         10579
_refine_ls_number_restraints     1706
_refine_ls_restrained_S_all      0.949
_refine_ls_R_factor_all          0.1613
_refine_ls_R_factor_gt           0.1309
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1791P)^2^+332.0431P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3314
_refine_ls_wR_factor_ref         0.3600
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7691
_reflns_number_total             10579
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02482b2.cif
_cod_data_source_block           MUV27-py-CH3
_cod_original_cell_volume        10114.8(10)
_cod_database_code               7713773
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.932
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.749(4)
 0.251(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 N8-C82 = N8-C83
 1.45 with sigma of 0.02
 C82-C83
 2.4 with sigma of 0.02
 C21-C16
 1.45 with sigma of 0.02
 Mo4-N4 \\sim Mo4-N0
 with sigma of 0.02
 C69-C70 \\sim C63-C64
 with sigma of 0.02
 N4-C38 \\sim N0-C32
 with sigma of 0.02
 N4-C28 \\sim N0-C34
 with sigma of 0.02
 Mo6-C67 \\sim Mo6-C61
 with sigma of 0.04
 C66-C68 \\sim C72-C62
 with sigma of 0.04
 N7-C71 \\sim N6-C65
 with sigma of 0.02
 C38-C37 \\sim C32-C31
 with sigma of 0.02
 C37-C30 \\sim C31-C36
 with sigma of 0.02
 C28-C29 \\sim C34-C35
 with sigma of 0.02
 C30-C33 \\sim C36-C60
 with sigma of 0.02
 C30-C29 \\sim C36-C35
 with sigma of 0.02
 N7-C70 \\sim N6-C64
 with sigma of 0.04
 C69-C71 \\sim C63-C65
 with sigma of 0.04
 Mo4-C38 \\sim Mo4-C32
 with sigma of 0.04
 Mo4-C28 \\sim Mo4-C34
 with sigma of 0.04
 C70-C68 \\sim C64-C62
 with sigma of 0.04
 N4-C37 \\sim N0-C31
 with sigma of 0.04
 N4-C29 \\sim N0-C35
 with sigma of 0.04
 N7-C67 \\sim N6-C61
 with sigma of 0.02
 C38-C28 \\sim C32-C34
 with sigma of 0.04
 C69-C66 \\sim C63-C72
 with sigma of 0.02
 C38-C30 \\sim C32-C36
 with sigma of 0.04
 C69-C68 \\sim C63-C62
 with sigma of 0.02
 C67-C68 \\sim C61-C62
 with sigma of 0.02
 C71-C70 \\sim C65-C64
 with sigma of 0.02
 C37-C33 \\sim C31-C60
 with sigma of 0.04
 C37-C29 \\sim C31-C35
 with sigma of 0.04
 Mo6-C71 \\sim Mo6-C65
 with sigma of 0.04
 N7-C68 \\sim N6-C62
 with sigma of 0.04
 C69-C67 \\sim C63-C61
 with sigma of 0.04
 C28-C30 \\sim C34-C36
 with sigma of 0.04
 C67-C71 \\sim C61-C65
 with sigma of 0.04
 C66-C70 \\sim C72-C64
 with sigma of 0.04
 C33-C29 \\sim C60-C35
 with sigma of 0.04
 Mo6-N7 \\sim Mo6-N6
 with sigma of 0.02
 C52-C51 \\sim C57-C56
 with sigma of 0.02
 C52-C50 \\sim C57-C55
 with sigma of 0.04
 C50-C59 \\sim C55-C58
 with sigma of 0.02
 C50-C48 \\sim C55-C53
 with sigma of 0.04
 C50-C51 \\sim C55-C56
 with sigma of 0.02
 N5-C52 \\sim N5-C57
 with sigma of 0.02
 C49-C48 \\sim C54-C53
 with sigma of 0.02
 N5-C49 \\sim N5-C54
 with sigma of 0.04
 C51-C59 \\sim C56-C58
 with sigma of 0.04
 N5-C51 \\sim N5-C56
 with sigma of 0.04
 C49-C51 \\sim C54-C56
 with sigma of 0.04
 C49-C59 \\sim C54-C58
 with sigma of 0.04
 N5-C48 \\sim N5-C53
 with sigma of 0.02
 C49-C50 \\sim C54-C55
 with sigma of 0.02
4. Restrained planarity
 N6, C63, C61, C65, C72, C64, C62
 with sigma of 0.1
 C59, C50, C51, C49, C48, N5, C52
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
N4 \\sim C38 \\sim C37 \\sim C28 \\sim C30 \\sim C33 \\sim C29 \\sim N0 \\sim
C32 \\sim C31 \\sim C34 \\sim C36 \\sim C60 \\sim C35: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
N7 \\sim C69 \\sim C67 \\sim C71 \\sim C66 \\sim C70 \\sim C68 \\sim N6 \\sim
C63 \\sim C61 \\sim C65 \\sim C72 \\sim C64 \\sim C62: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
N5 \\sim C49 \\sim C52 \\sim C50 \\sim C48 \\sim C51 \\sim C59 \\sim C53 \\sim
C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 2A
C52 \\sim C57: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
6. Rigid body (RIGU) restrains
 C37, Mo6, O24, O22, O21, O25, N7, Mo5, C73, C67, C71, O23, O18, N5, C74, O26,
 C68, C70, C47, C52, C48, C79, C75, C69, O17, C44, C51, C49, C78, C76, C66, C43,
  C45, C50, C77, C81, C80, C42, C40, C59, O29, O30, O27, O28, C46, C41, C39,
 Mo1, O19, O20, O16, O15, O3, O1, O2, N1, Mo2, Mo4, C5, C1, O5, N2, O4, O14,
 O12, O11, N4, Mo3, C4, C2, C13, C7, C11, C38, C28, O13, O10, N3, C3, O6, C14,
 C8, C10, C29, C21, C26, C22, C6, C15, C19, C9, C30, C16, O9, C25, C23, C18,
 C12, C33, C17, C24, C20, C27, O7, O8
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 N6, C63, C61, C65, C72, C64, C62
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N0, C32, C31, C34, C36, C60, C35
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4, C38, C37, C28, C30, C33, C29
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N7, C69, C67, C71, C66, C70, C68
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C54, C57, C55, C53, C56, C58
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C49, C52, C50, C48, C51, C59
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C5S, C4S, N3S, C2S, O1S
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
7. Others
 Sof(C31)=Sof(H31)=Sof(C36)=Sof(C35)=Sof(H35)=Sof(C34)=Sof(H34)=Sof(N0)=
 Sof(C32)=Sof(H32)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=1-FVAR(1)
 Sof(N4)=Sof(C38)=Sof(H38)=Sof(C37)=Sof(H37)=Sof(C28)=Sof(H28)=Sof(C30)=
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C29)=Sof(H29)=FVAR(1)
 Sof(N6)=Sof(C63)=Sof(C61)=Sof(H61)=Sof(C65)=Sof(H65)=Sof(C72)=Sof(H72A)=
 Sof(H72B)=Sof(H72C)=Sof(C64)=Sof(H64)=Sof(C62)=Sof(H62)=1-FVAR(2)
 Sof(N7)=Sof(C71)=Sof(H71)=Sof(C70)=Sof(H70)=Sof(C69)=Sof(C68)=Sof(H68)=
 Sof(C67)=Sof(H67)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=FVAR(2)
 Sof(C53)=Sof(H53)=Sof(C54)=Sof(H54)=Sof(C55)=Sof(C56)=Sof(H56)=Sof(C57)=
 Sof(H57)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=1-FVAR(3)
 Sof(C49)=Sof(H49)=Sof(C52)=Sof(H52)=Sof(C50)=Sof(C48)=Sof(H48)=Sof(C51)=
 Sof(H51)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=FVAR(3)
8.a Secondary CH2 refined with riding coordinates:
 N9(H9A,H9B), N8(H8A,H8B), N10(H10A,H10B)
8.b Me refined with riding coordinates:
 C12(H12A,H12B,H12C), C4S(H4SA,H4SB,H4SC), C6(H6A,H6B,H6C), C83(H83A,H83B,
 H83C), C86(H86A,H86B,H86C), C85(H85A,H85B,H85C), C84(H84A,H84B,H84C), C27(H27A,
 H27B,H27C), C66(H66A,H66B,H66C), C33(H33A,H33B,H33C), C59(H59A,H59B,H59C),
 C87(H87A,H87B,H87C), C82(H82A,H82B,H82C), C60(H60A,H60B,H60C), C72(H72A,H72B,
 H72C), C5S(H5SA,H5SB,H5SC), C58(H58A,H58B,H58C)
8.c Aromatic/amide H refined with riding coordinates:
 C71(H71), C70(H70), C68(H68), C67(H67), C43(H43), C45(H45), C77(H77),
 C79(H79), C49(H49), C52(H52), C41(H41), C8(H8), C15(H15), C5(H5), C1(H1),
 C10(H10), C75(H75), C17(H17), C19(H19), C2(H2), C7(H7), C38(H38), C48(H48),
 C26(H26), C11(H11), C4(H4), C25(H25), C37(H37), C22(H22), C51(H51), C28(H28),
 C23(H23), C29(H29), C2S(H2S), C31(H31), C35(H35), C34(H34), C32(H32), C61(H61),
  C65(H65), C64(H64), C62(H62), C53(H53), C54(H54), C56(H56), C57(H57)
8.d Fitted hexagon refined as free rotating group:
 N7(C71,C70,C69,C68,C67), C31(C36,C35,C34,N0,C32)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 638 electrons were 
found in a volume of 2456\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
4[C3H7NO], 4[C3H7NO] per Formula Unit 
which account for 640 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              92625
_shelx_fab_checksum              74037
_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 1.268
_oxdiff_exptl_absorpt_empirical_full_min 0.846