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_7713772
_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
'C110 H92 Mo12 N22 O62, 6.037(C2 H8 N), 1.743(C5 H6 N2), 2(C1.227 H3.435 N0.491 O0.491)'
_chemical_formula_sum            'C133.21 H157.62 Mo12 N32.49 O62.98'
_chemical_formula_weight         4372.86
_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
_audit_creation_date             2022-12-06
_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                 108.715(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   19.0877(7)
_cell_length_b                   18.2843(6)
_cell_length_c                   26.7480(7)
_cell_measurement_reflns_used    10889
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      16.1710
_cell_measurement_theta_min      3.0830
_cell_volume                     8841.6(5)
_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 2018/2 (Sheldrick, 2018)'
_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 0.995
_diffrn_measured_fraction_theta_max 0.995
_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    -88.00  58.00   1.00   20.00    --  -14.73   0.00 -90.00  146
  2  \w    -40.00  58.00   1.00   20.00    --  -14.73  38.00 -30.00   98
  3  \w    -78.00 -11.00   1.00   20.00    --  -14.73 134.00 145.62   67
  4  \w    -84.00   7.00   1.00   20.00    --  -14.73 -57.00  30.00   91
  5  \w    -57.00  41.00   1.00   20.00    --   15.75 -38.00  60.00   98
  6  \w    -14.00  42.00   1.00   20.00    --   15.75  77.00 -90.00   56
  7  \w     -6.00  85.00   1.00   20.00    --   15.75  57.00-180.00   91
  8  \w    -14.00  42.00   1.00   20.00    --   15.75  77.00 -30.00   56
  9  \w    -42.00  46.00   1.00   20.00    --   15.75 -77.00  30.00   88
 10  \w      8.00  76.00   1.00   20.00    --   15.75-129.00  55.45   68
 11  \w    -42.00  15.00   1.00   20.00    --  -14.73 -77.00  90.00   57
 12  \w    -91.00 -37.00   1.00   20.00    --  -14.73 178.00 -90.00   54
 13  \w    -78.00 -11.00   1.00   20.00    --  -14.73 134.00  41.13   67
 14  \w    -78.00 -48.00   1.00   20.00    --  -14.73 134.00 -79.00   30
 15  \w    -15.00  58.00   1.00   20.00    --   15.75 -99.00 -60.00   73
 16  \w     -6.00  85.00   1.00   20.00    --   15.75  57.00-120.00   91
 17  \w    -57.00  41.00   1.00   20.00    --   15.75 -38.00 150.00   98
 18  \w    -14.00  42.00   1.00   20.00    --   15.75  77.00   0.00   56
;
_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      -0.0333136000
_diffrn_orient_matrix_UB_12      -0.0120675000
_diffrn_orient_matrix_UB_13      0.0036835000
_diffrn_orient_matrix_UB_21      -0.0026468000
_diffrn_orient_matrix_UB_22      0.0335800000
_diffrn_orient_matrix_UB_23      0.0125557000
_diffrn_orient_matrix_UB_31      -0.0205453000
_diffrn_orient_matrix_UB_32      0.0152307000
_diffrn_orient_matrix_UB_33      -0.0247561000
_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  0.1320
_diffrn_reflns_av_unetI/netI     0.0487
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            102160
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        17.226
_diffrn_reflns_theta_max         17.226
_diffrn_reflns_theta_min         2.851
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.912
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91485
_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    1.643
_exptl_crystal_description       plate
_exptl_crystal_F_000             4384
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.815
_refine_diff_density_min         -0.505
_refine_diff_density_rms         0.118
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     658
_refine_ls_number_reflns         5318
_refine_ls_number_restraints     306
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.1136
_refine_ls_R_factor_gt           0.0810
_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^)+(0.1305P)^2^+112.6222P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2114
_refine_ls_wR_factor_ref         0.2415
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3826
_reflns_number_total             5318
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02482b2.cif
_cod_data_source_block           MUV27-py-NH2-act
_cod_database_code               7713772
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.982
_shelx_estimated_absorpt_t_min   0.947
_olex2_refinement_description
;
1. 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
2. Restrained distances
 N15-C73 = N15-C69
 1.45 with sigma of 0.02
 C69-C73
 2.4 with sigma of 0.02
 C66-N18
 1.45 with sigma of 0.02
 N4-C8
 1.45 with sigma of 0.02
 C24-C21
 1.45 with sigma of 0.02
 C75-C74
 2.4 with sigma of 0.02
 N19-C75 = N19-C74
 1.45 with sigma of 0.02
 C72-C1B
 2.4 with sigma of 0.02
 C1A-C72
 2.4 with sigma of 0.02
 N5W-C16 = N5W-C70
 1.45 with sigma of 0.02
 C70-C16
 2.4 with sigma of 0.02
 O25-O1A
 -3 with sigma of 0.02
 C9-N4 \\sim N4-C7
 with sigma of 0.02
 C67-N18 \\sim N18-C65
 with sigma of 0.02
 C9-N4 \\sim C12-H4A
 with sigma of 0.04
 C8-N4 \\sim C13-H4A
 with sigma of 0.02
 O31-Mo5 \\sim Mo5-O32
 with sigma of 0.002
 C7-N4 \\sim C14-H4A
 with sigma of 0.04
 N13-C48 \\sim N13-C49
 with sigma of 0.02
 C10-C9 \\sim C11-C12
 with sigma of 0.02
 C7-C8 \\sim C14-C13
 with sigma of 0.02
 N3-C9 \\sim N5-C12
 with sigma of 0.04
 C10-N3 \\sim C11-N5
 with sigma of 0.02
 C6-C8 \\sim C15-C13
 with sigma of 0.04
 C7-C9 \\sim C14-C12
 with sigma of 0.04
 Mo2-N3 \\sim Mo2-N5
 with sigma of 0.02
 C8-C9 \\sim C13-C12
 with sigma of 0.02
 Mo2-C10 \\sim Mo2-C11
 with sigma of 0.04
 Mo2-C6 \\sim Mo2-C15
 with sigma of 0.04
 N3-C6 \\sim N5-C15
 with sigma of 0.02
 C10-C6 \\sim C11-C15
 with sigma of 0.04
 C10-C8 \\sim C11-C13
 with sigma of 0.04
 C6-C7 \\sim C15-C14
 with sigma of 0.02
 N3-C7 \\sim N5-C14
 with sigma of 0.04
 C24-C21 \\sim C17-C71 \\sim C23-C19
 with sigma of 0.002
 C74-C75 \\sim C74A-C75A
 with sigma of 0.04
 C74-N19 \\sim C74A-N19A
 with sigma of 0.02
 N19-C75 \\sim N19A-C75A
 with sigma of 0.02
3. Restrained planarity
 N4, C8, C9, C10, N3, C6, C7
 with sigma of 0.1
 C44, O32, N14, C45, C46
 with sigma of 0.1
 C47, O31, N13, C48, C49
 with sigma of 0.1
 C1A, O1A, N16, C1B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C26 \\sim C25 \\sim N7 \\sim C29 \\sim C28 \\sim C27 \\sim N8: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C64 \\sim C65 \\sim C66 \\sim N18 \\sim C67 \\sim C68 \\sim N17: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C44 \\sim O32 \\sim N14 \\sim C45 \\sim C46: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C44 \\sim O32 \\sim N14 \\sim C45 \\sim C46 \\sim C47 \\sim O31 \\sim N13 \\sim
C48 \\sim C49: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
C47 \\sim O31 \\sim N13 \\sim C48 \\sim C49: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C10 \\sim N3 \\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim N4 \\sim C11 \\sim C12
\\sim C13 \\sim H4A \\sim C14 \\sim C15 \\sim N5: within 2A with sigma of 0.02
and sigma for terminal atoms of 0.04 within 2A
C74 \\sim N19 \\sim C75: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 2A
C75 \\sim C74 \\sim N19 \\sim N19A \\sim C74A \\sim C75A: within 2A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 2A
N16 \\sim C72 \\sim C1B \\sim C1A \\sim O1A \\sim C69 \\sim N15 \\sim C73:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C1A \\sim O1A \\sim N16 \\sim C1B: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C33 \\sim C34 \\sim N9 \\sim C30 \\sim C31 \\sim C32: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
5. Rigid body (RIGU) restrains
 C44, O32, N14, C45, C46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N7, Mo6, O11, O10, O9, O26, N11, Mo5, C55, C54, C50, O12, O23, O32, O31, O25,
 C56, C53, C51, C43, C44, C47, C57, C61, C52, O24, C40, N14, N13, C58, C60, N12,
  C39, C41, C45, C46, C48, C49, C62, C59, C63, C38, C36, O28, O27, O29, O30,
 C42, C37, C35, Mo1, O21, O22, O20, O19, Mo2, O1, O2, O3, N1, Mo4, O13, O4, C1,
 C5, Mo3, O5, O6, N9, O8, C71, C2, C4, O16, O7, C30, C34, O14, C17, C3, C23,
 C25, C29, C31, C33, C22, C18, N2, O15, C19, C26, C28, C32, C21, C20, C27, N10,
 C24, N8, O18, O17
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11, N5, C15, C14, C13, C12, H4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C10, N3, C6, C7, C8, C9, N4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C47, O31, N13, C48, C49
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C74A, N19A, C75A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C74, N19, C75
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, O1A, N16, C1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C47)=Sof(H47)=Sof(O31)=Sof(N13)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=
 Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=1-FVAR(1)
 Sof(C44)=Sof(H44)=Sof(O32)=Sof(N14)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=
 Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=FVAR(1)
 Sof(N18)=Sof(H18A)=Sof(H18B)=Sof(C64)=Sof(H64)=Sof(C65)=Sof(H65)=Sof(C66)=
 Sof(C67)=Sof(H67)=Sof(C68)=Sof(H68)=Sof(N17)=FVAR(2)
 Sof(C11)=Sof(H11)=Sof(N5)=Sof(C15)=Sof(H15)=Sof(C14)=Sof(H14)=Sof(C13)=
 Sof(C12)=Sof(H12)=Sof(N6)=Sof(H6A)=Sof(H6B)=1-FVAR(3)
 Sof(C10)=Sof(H10)=Sof(N3)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(C9)=
 Sof(H9)=Sof(N4)=Sof(H4A)=Sof(H4B)=FVAR(3)
 Sof(C75A)=Sof(H75D)=Sof(H75E)=Sof(H75F)=Sof(N19A)=Sof(H19C)=Sof(H19D)=
 Sof(C74A)=Sof(H74D)=Sof(H74E)=Sof(H74F)=1-FVAR(4)
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=Sof(N19)=Sof(H19A)=Sof(H19B)=Sof(C75)=
 Sof(H75A)=Sof(H75B)=Sof(H75C)=FVAR(4)
 Sof(H72A)=Sof(H72B)=Sof(H72C)=Sof(C1A)=Sof(H1A)=Sof(O1A)=Sof(N16)=Sof(C1B)=
 Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=1-FVAR(5)
 Sof(C72)=0.5*(1-FVAR(6))
 Sof(N5W)=Sof(H5WA)=Sof(H5WB)=Sof(N15)=Sof(H15A)=Sof(H15B)=Sof(C73)=Sof(H73A)=
 Sof(H73B)=Sof(H73C)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C16)=Sof(H16A)=
 Sof(H16B)=Sof(H16C)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=FVAR(5)
7.a Riding coordinates:
 N2(H2A,H2B), C23D(H23A,H23B,H23C), N12(H12A,H12B), N10(H10A,H10B), N8(H8A,
 H8B), N18(H18A,H18B), N4(H4A,H4B), N6(H6A,H6B)
7.b Free rotating group:
 C44(O32,N14,C45,C46), C47(O31,N13,C48,C49), C1A(O1A,N16,C1B)
7.c Secondary CH2 refined with riding coordinates:
 N22D(H22A,H22B), N5W(H5WA,H5WB), N15(H15A,H15B), N19(H19A,H19B), N19A(H19C,
 H19D)
7.d Me refined with riding coordinates:
 C24D(H24A,H24B,H24C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C48(H48A,H48B,
 H48C), C49(H49A,H49B,H49C), C73(H73A,H73B,H73C), C72(H72A,H72B,H72C), C69(H69A,
 H69B,H69C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C75A(H75D,H75E,H75F),
 C74A(H74D,H74E,H74F), C1B(H1BA,H1BB,H1BC), C16(H16A,H16B,H16C), C70(H70A,H70B,
 H70C)
7.e Aromatic/amide H refined with riding coordinates:
 C54(H54), C53(H53), C51(H51), C50(H50), C30(H30), C31(H31), C33(H33),
 C34(H34), C57(H57), C61(H61), C25(H25), C26(H26), C28(H28), C29(H29), C39(H39),
  C41(H41), C37(H37), C22(H22), C1(H1), C18(H18), C20(H20), C59(H59), C4(H4),
 C2(H2), C5(H5), C44(H44), C47(H47), C64(H64), C65(H65), C67(H67), C68(H68),
 C10(H10), C6(H6), C7(H7), C9(H9), C11(H11), C15(H15), C14(H14), C12(H12),
 C1A(H1A)
7.f Fitted hexagon refined as free rotating group:
 N11(C54,C53,C52,C51,C50), N9(C30,C31,C32,C33,C34), N7(C25,C26,C27,C28,C29),
 C64(C65,C66,C67,C68,N17), C10(N3,C6,C7,C8,C9), C11(N5,C15,C14,C13,C12)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 44 electrons were 
found in a volume of 266\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
0.5[CH2Cl2] per Formula Unit 
which account for 42 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              83850
_shelx_fab_checksum              33538
_olex2_date_sample_data_collection 2022-09-30
_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 1.140
_oxdiff_exptl_absorpt_empirical_full_min 0.858