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_7719790
_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         'C80 H88 F Mn4 O24 S8, C16 H36 N'
_chemical_formula_sum            'C96 H124 F Mn4 N O24 S8'
_chemical_formula_weight         2171.19
_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_Hall           '-C 2y'
_space_group_name_H-M_alt        'C 1 2/m 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2020-09-29
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2025-02-19 deposited with the CCDC.	2025-11-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.275(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   21.3377(11)
_cell_length_b                   13.4040(6)
_cell_length_c                   18.9593(13)
_cell_measurement_reflns_used    6705
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      28.7450
_cell_measurement_theta_min      3.0990
_cell_volume                     5178.0(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.2634
_diffrn_detector_type            Onyx
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.869
_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     -7.00  70.00   1.00  425.00    --    8.26  37.00  30.00   77
  2  \w    -72.00  58.00   1.00  425.00    --    8.26   0.00-150.00  130
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Onyx'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0166788000
_diffrn_orient_matrix_UB_12      0.0336337000
_diffrn_orient_matrix_UB_13      0.0282288000
_diffrn_orient_matrix_UB_21      -0.0135618000
_diffrn_orient_matrix_UB_22      -0.0244807000
_diffrn_orient_matrix_UB_23      0.0252673000
_diffrn_orient_matrix_UB_31      0.0273458000
_diffrn_orient_matrix_UB_32      -0.0326907000
_diffrn_orient_matrix_UB_33      0.0100634000
_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  0.0391
_diffrn_reflns_av_unetI/netI     0.0506
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.869
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            17320
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.869
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.553
_diffrn_reflns_theta_min         3.116
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.709
_exptl_absorpt_correction_T_max  0.979
_exptl_absorpt_correction_T_min  0.887
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (Rigaku Oxford Diffraction, 2019)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.393
_exptl_crystal_description       plate
_exptl_crystal_F_000             2272
_exptl_crystal_size_max          0.204
_exptl_crystal_size_mid          0.175
_exptl_crystal_size_min          0.033
_refine_diff_density_max         1.281
_refine_diff_density_min         -0.851
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     368
_refine_ls_number_reflns         6565
_refine_ls_number_restraints     309
_refine_ls_restrained_S_all      1.114
_refine_ls_R_factor_all          0.0890
_refine_ls_R_factor_gt           0.0632
_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^)+(0.1084P)^2^+15.0170P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1796
_refine_ls_wR_factor_ref         0.2013
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4696
_reflns_number_total             6565
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02234g2.cif
_cod_data_source_block           tbu_mn
_cod_depositor_comments
'Adding full bibliography for 7719790--7719792.cif.'
_cod_original_cell_volume        5177.9(5)
_cod_database_code               7719790
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C96 H124 F1 Mn4 N1 O24 S8'
_reflns_odcompleteness_completeness 99.76
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
 C30-C32
 1.5 with sigma of 0.01
 C29-C30
 1.5 with sigma of 0.01
 C29-C31
 1.5 with sigma of 0.01
 N1-C31
 1.5 with sigma of 0.01
 N1-C26
 1.5 with sigma of 0.01
 C25-C26
 1.5 with sigma of 0.01
 C25-C27
 1.5 with sigma of 0.01
 C27-C28
 1.5 with sigma of 0.01
 C26-C27
 2.55 with sigma of 0.01
 C29-N1
 2.55 with sigma of 0.01
 C31-C26
 2.55 with sigma of 0.01
 C25-C28
 2.55 with sigma of 0.01
 C32-C29
 2.55 with sigma of 0.01
 C30-C31
 2.55 with sigma of 0.01
3. Restrained planarity
 N1, C25, C26, C27, C28
 with sigma of 0.1
 N1, C29, C30, C31, C32
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C19 \\sim C15 \\sim C18 \\sim C9 \\sim C11 \\sim C8 \\sim C1 \\sim O1 \\sim S2
\\sim O7 \\sim O5 \\sim C20 \\sim C17 \\sim C22 \\sim C23 \\sim C14 \\sim C12
\\sim C4 \\sim C3 \\sim C5 \\sim C13 \\sim C21 \\sim C16 \\sim C24 \\sim C6
\\sim C10 \\sim C2 \\sim C7 \\sim S1 \\sim O2 \\sim O4 \\sim O6 \\sim O3 \\sim
F1 \\sim Mn1: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
N1 \\sim C25 \\sim C26 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim
C27: within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
1.7A
5. Rigid body (RIGU) restrains
 N1, C25, C26, C29, C30, C31, C32, C27, C28
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Others
 Fixed Sof: H19A(0.5) H19B(0.5) H19C(0.5) H24A(0.5) H24B(0.5) H24C(0.5)
 C25(0.5) H25A(0.5) H25B(0.5) C26(0.5) H26A(0.5) H26B(0.5) C27(0.5) H27A(0.5)
 H27B(0.5) C28(0.5) H28A(0.5) H28B(0.5) H28C(0.5) C29(0.5) H29A(0.5) H29B(0.5)
 C30(0.5) H30A(0.5) H30B(0.5) C31(0.5) H31A(0.5) H31B(0.5) C32(0.5) H32A(0.5)
 H32B(0.5) H32C(0.5)
 Fixed X: N1(0.5)
 Fixed Y: N1(0)
 Fixed Z: N1(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C29(H29A,H29B), C30(H30A,
 H30B), C31(H31A,H31B)
7.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13)
7.c Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C28(H28A,
 H28B,H28C), C32(H32A,H32B,H32C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_date_sample_data_collection 2020-09-25
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a nylon loop in perfluoroether oil'
_olex2_submission_original_sample_id tbu_mn
_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 1.107
_oxdiff_exptl_absorpt_empirical_full_min 0.955