Multiphoton excitation and energy transfer pathways in Mn<sup>2+</sup>-sulfonyl calixarene complexes.
Lecourt, Constance; Ledoux, Gilles; Suffren, Yan; Jeanneau, Erwann; Luneau, Dominique; Desroches, Cedric; Dalton transactions (Cambridge, England : 2003) 54 (2025) 17151–17161; doi:10.1039/d5dt02234g

data_7719791
_publ_section_title
;
 Multiphoton excitation and energy transfer pathways in
 Mn<sup>2+</sup>-sulfonyl calixarene complexes.
;
_journal_issue                   46
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              17151
_journal_page_last               17161
_journal_paper_doi               10.1039/d5dt02234g
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C112 H56 F Mn4 O24 S8, 2(C16 H36 N)'
_chemical_formula_sum            'C144 H128 F Mn4 N2 O24 S8'
_chemical_formula_weight         2765.72
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-10-25
_audit_creation_method
;
Olex2 1.5-ac6-012
(compiled 2023.08.24 svn.re1ec1418 for Rigaku Oxford Diffraction, GUI svn.r6817)
;
_audit_update_record
;
2025-02-19 deposited with the CCDC.	2025-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                92.025(9)
_cell_angle_beta                 93.088(10)
_cell_angle_gamma                101.882(15)
_cell_formula_units_Z            1
_cell_length_a                   12.449(2)
_cell_length_b                   14.778(2)
_cell_length_c                   18.3713(15)
_cell_measurement_reflns_used    4082
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      21.7600
_cell_measurement_theta_min      3.3880
_cell_volume                     3298.8(8)
_computing_cell_refinement       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 40.82a (release 26-06-2020))'
_computing_data_reduction        'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac6-012 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-012 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4685
_diffrn_detector_type            Atlas
_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    -90.00  31.00   1.00  165.00    --  -10.24 -19.00 -60.00  121
  2  \w    -38.00  63.00   1.00  165.00    --  -10.24  57.00-120.00  101
  3  \w    -43.00  39.00   1.00  165.00    --  -10.24  77.00-150.00   82
  4  \w    -63.00  33.00   1.00  165.00    --   11.34 -37.00-150.00   96
  5  \w    -20.00  34.00   1.00  165.00    --   11.34  77.00-120.00   54
  6  \w    -36.00  28.00   1.00  165.00    --   11.34 -62.00 115.00   64
  7  \w    -12.00  65.00   1.00  165.00    --   11.34  37.00   0.00   77
  8  \w    -19.00  32.00   1.00  165.00    --   11.34  77.00  90.00   51
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0257353000
_diffrn_orient_matrix_UB_12      0.0274765000
_diffrn_orient_matrix_UB_13      -0.0276004000
_diffrn_orient_matrix_UB_21      0.0393278000
_diffrn_orient_matrix_UB_22      -0.0284146000
_diffrn_orient_matrix_UB_23      -0.0021251000
_diffrn_orient_matrix_UB_31      -0.0345588000
_diffrn_orient_matrix_UB_32      -0.0291348000
_diffrn_orient_matrix_UB_33      -0.0270571000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0767
_diffrn_reflns_av_unetI/netI     0.0488
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            13817
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        14.704
_diffrn_reflns_theta_max         14.704
_diffrn_reflns_theta_min         2.699
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.574
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95069
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.92a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.392
_exptl_crystal_description       needle
_exptl_crystal_F_000             1435
_exptl_crystal_size_max          0.37
_exptl_crystal_size_mid          0.045
_exptl_crystal_size_min          0.039
_refine_diff_density_max         0.485
_refine_diff_density_min         -0.602
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     830
_refine_ls_number_reflns         2503
_refine_ls_number_restraints     1459
_refine_ls_restrained_S_all      0.853
_refine_ls_R_factor_all          0.1022
_refine_ls_R_factor_gt           0.0864
_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^)+(0.1757P)^2^+47.6809P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2387
_refine_ls_wR_factor_ref         0.2581
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1999
_reflns_number_total             2503
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02234g2.cif
_cod_data_source_block           ac_2
_cod_depositor_comments
'Adding full bibliography for 7719790--7719792.cif.'
_cod_original_cell_volume        3298.8(9)
_cod_database_code               7719791
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.978
_shelx_estimated_absorpt_t_min   0.816
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C67-C7 = C35-C7 = C35-C15 = C69-C15 = C71-C69 = C71-C67 = C5-C19 = C23-C5 =
 C17-C19 = C17-C33 = C33-C53 = C53-C23
 1.4 with sigma of 0.02
 C53-C23 \\sim C23-C5 \\sim C5-C19 \\sim C17-C19 \\sim C17-C33 \\sim C33-C53
\\sim C71-C67 \\sim C67-C7 ~
 C35-C7 \\sim C35-C15 \\sim C69-C15 \\sim C71-C69
 with sigma of 0.01
 C57-C3 \\sim C25-C3 \\sim C25-C47 \\sim C41-C39 \\sim C21-C41 \\sim C61-C21
\\sim C55-C49 \\sim C49-C45 ~
 C31-C45 \\sim C59-C43 \\sim C13-C11 \\sim C59-C13
 with sigma of 0.01
 N1-C55 \\sim N1-C47 \\sim N1-C39 \\sim N1-C11
 with sigma of 0.01
3. Restrained planarity
 C7, C15, C35, C67, C69, C71
 with sigma of 0.1
 C5, C17, C19, C23, C33, C53
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
N1 \\sim C3 \\sim C21 \\sim C25 \\sim C31 \\sim C39 \\sim C41 \\sim C43 \\sim
C45 \\sim C47 \\sim C49 \\sim C55 \\sim C57 \\sim C59 \\sim C61: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Mn1 \\sim Mn2 \\sim S1 \\sim S2 \\sim S3 \\sim S4 \\sim F1 \\sim O1 \\sim O2
\\sim O3 \\sim O4 \\sim O5 \\sim O6 \\sim O7 \\sim O8 \\sim O9 \\sim O10 \\sim
O11 \\sim O12 \\sim C1 \\sim C2 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8
\\sim C9 \\sim C10 \\sim C12 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18
\\sim C19 \\sim C20 \\sim C22 \\sim C23 \\sim C24 \\sim C26 \\sim C27 \\sim C28
\\sim C29 \\sim C30 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37
\\sim C38 \\sim C40 \\sim C42 \\sim C44 \\sim C46 \\sim C48 \\sim C50 \\sim C51
\\sim C52 \\sim C53 \\sim C54 \\sim C56 \\sim C58 \\sim C60 \\sim C62 \\sim C63
\\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71
\\sim C72: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
Uanis(C40) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(O10)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 N1, C3, C13, C21, C25, C31, C39, C41, C43, C45, C47, C49, C55, C57, C59, C61
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Mn1, Mn2, S1, S2, S3, S4, F1, O1, O2, O3, O4, O5, O6, O7, O8, O9, O10, O11,
 O12, C1, C2, C4, C5, C6, C7, C8, C9, C10, C12, C14, C15, C16, C17, C18, C19,
 C20, C22, C23, C24, C26, C27, C28, C29, C30, C32, C33, C34, C35, C36, C37, C38,
  C40, C42, C44, C46, C48, C50, C51, C52, C53, C54, C56, C58, C60, C62, C63,
 C64, C65, C66, C67, C68, C69, C70, C71, C72
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C11(H11A,H11B), C13(H13A,H13B), C21(H21A,H21B), C25(H25A,H25B),
 C39(H39A,H39B), C41(H41A,H41B), C45(H45A,H45B), C47(H47A,H47B), C49(H49A,H49B),
  C55(H55A,H55B), C59(H59A,H59B)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C5(H5), C7(H7), C15(H15), C16(H16), C17(H17), C23(H23), C27(H27),
 C30(H30), C32(H32), C33(H33), C35(H35), C36(H36), C40(H40), C44(H44), C46(H46),
  C48(H48), C51(H51), C53(H53), C58(H58), C62(H62), C63(H63), C65(H65),
 C66(H66), C68(H68), C69(H69), C70(H70), C71(H71)
6.c Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C43(H43A,H43B,H43C), C57(H57A,H57B,H57C), C61(H61A,H61B,
 H61C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              25021
_shelx_hkl_checksum              1522
_shelx_fab_checksum              19113
_olex2_date_sample_data_collection 2022-05-06
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id Ac
_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 1.204
_oxdiff_exptl_absorpt_empirical_full_min 0.879