Distal scaffold flexibility accelerates ligand substitution kinetics in manganese(I) tricarbonyls: flexible thianthrene <i>versus</i> rigid anthracene scaffolds.
Labrecque, Jordan; Cho, Yae-In; McIntosh, Daniel K.; Agboola, Faridat; Rose, Michael J.; Dalton transactions (Cambridge, England : 2003)  (2023) –; doi:10.1039/d2dt04048d

data_7712529
_publ_section_title
;
 Distal scaffold flexibility accelerates ligand substitution kinetics in
 manganese(I) tricarbonyls: flexible thianthrene <i>versus</i> rigid
 anthracene scaffolds.
;
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/d2dt04048d
_journal_year                    2023
_chemical_formula_moiety         'C25 H14 Br Mn N2 O3 S2, C4 H8 O'
_chemical_formula_sum            'C29 H22 Br Mn N2 O4 S2'
_chemical_formula_weight         661.45
_chemical_name_systematic        (thianth-py2)Mn(CO)3Br
_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             2021-12-18
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-06-23 deposited with the CCDC.	2023-02-23 downloaded from the CCDC.
;
_cell_angle_alpha                74.444(2)
_cell_angle_beta                 80.984(2)
_cell_angle_gamma                76.153(2)
_cell_formula_units_Z            2
_cell_length_a                   8.7988(2)
_cell_length_b                   9.5552(3)
_cell_length_c                   17.5608(4)
_cell_measurement_reflns_used    9511
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      27.5140
_cell_measurement_theta_min      2.2290
_cell_volume                     1374.22(6)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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      100.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_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   -110.00  24.00   0.50   45.00    --  -20.00 -60.00 240.00  268
  2  \w   -110.00  24.00   0.50   45.00    --  -20.00 -60.00 120.00  268
  3  \w   -110.00  70.00   0.50   45.00    --  -20.00   0.00   0.00  360
  4  \w    -50.00  70.00   0.50   45.00    --  -20.00  60.00  60.00  240
  5  \w    -50.00  70.00   0.50   45.00    --  -20.00  60.00 180.00  240
  6  \w    -50.00  62.50   0.50   45.00    --  -20.00  60.00 360.00  225
;
_diffrn_measurement_device       'Rigaku AFC-12 with a Satrun S2 CCD'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0758104000
_diffrn_orient_matrix_UB_12      -0.0013769000
_diffrn_orient_matrix_UB_13      0.0207245000
_diffrn_orient_matrix_UB_21      0.0286864000
_diffrn_orient_matrix_UB_22      -0.0724449000
_diffrn_orient_matrix_UB_23      0.0228589000
_diffrn_orient_matrix_UB_31      0.0197834000
_diffrn_orient_matrix_UB_32      0.0308868000
_diffrn_orient_matrix_UB_33      0.0286918000
_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  0.0723
_diffrn_reflns_av_unetI/netI     0.0785
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            25797
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         2.262
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.125
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87408
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.599
_exptl_crystal_description       plate
_exptl_crystal_F_000             668
_exptl_crystal_recrystallization_method 'vapor diffusion'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.028
_refine_diff_density_min         -0.708
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.130
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     407
_refine_ls_number_reflns         6305
_refine_ls_number_restraints     430
_refine_ls_restrained_S_all      1.109
_refine_ls_R_factor_all          0.1048
_refine_ls_R_factor_gt           0.0716
_refine_ls_shift/su_max          0.035
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0221P)^2^+5.9643P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1257
_refine_ls_wR_factor_ref         0.1357
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4687
_reflns_number_total             6305
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt04048d2.cif
_cod_data_source_block           thian_mnn2
_cod_database_code               7712529
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C18H20N2S2O4MnBr
_shelx_estimated_absorpt_t_max   0.920
_shelx_estimated_absorpt_t_min   0.785
_reflns_odcompleteness_completeness 99.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C25-O3 = C25A-O3A
 1.15 with sigma of 0.01
 Mn1-Br1 = Mn1-Br1A
 2.5 with sigma of 0.01
 Mn1-O3 = Mn1-O3A
 2.95 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O4 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim O4A \\sim C26A \\sim C27A
\\sim C28A \\sim C29A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
All non-hydrogen atoms restrained to be isotropic: with sigma of 0.01 and sigma
for terminal atoms of 0.02
4. Same fragment restrains
{O4, C26, C27, C28, C29} sigma for 1-2: 0.01, 1-3: 0.04
as in
{O4A, C26A, C27A, C28A, C29A}
5. Others
 Fixed Sof: O4(0.63) C26(0.63) H26A(0.63) H26B(0.63) C27(0.63) H27A(0.63)
 H27B(0.63) C28(0.63) H28A(0.63) H28B(0.63) C29(0.63) H29A(0.63) H29B(0.63)
 O4A(0.37) C26A(0.37) H26C(0.37) H26D(0.37) C27A(0.37) H27C(0.37) H27D(0.37)
 C28A(0.37) H28C(0.37) H28D(0.37) C29A(0.37) H29C(0.37) H29D(0.37) Br1(0.87)
 O3(0.87) C25(0.87) Br1A(0.13) O3A(0.13) C25A(0.13)
 Fixed Uiso: O3A(0.025) C25A(0.025)
6.a Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B), C26A(H26C,
 H26D), C27A(H27C,H27D), C28A(H28C,H28D), C29A(H29C,H29D)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C5(H5), C8(H8), C9(H9), C10(H10), C14(H14), C15(H15),
 C16(H16), C19(H19), C20(H20), C21(H21), C22(H22)
;
_shelx_res_checksum              28718
_shelx_hkl_checksum              37480
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.334
_oxdiff_exptl_absorpt_empirical_full_min 0.815