Antimony(+5) Ion Induced Tunable Intramolecular Charge Transfer in Hypervalent Antimony(V) Porphyrins
Holzer, Noah; Sharma, Jatan K.; Peterson, Steven; Bayard, Brandon J.; Nesterov, Vladimir; Karr, Paul A.; D'Souza, Francis; Poddutoori, Prashanth K.; Dalton Transactions  (2022) –; doi:10.1039/D2DT00675H

data_7709785
_publ_section_title
;
 Antimony(+5) Ion Induced Tunable Intramolecular Charge Transfer in
 Hypervalent Antimony(V) Porphyrins
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00675H
_journal_year                    2022
_chemical_formula_moiety         '2(C23 H17 N2 O Sb0.5), 3(C H Cl3), F6 P'
_chemical_formula_sum            'C49 H37 Cl9 F6 N4 O2 P Sb'
_chemical_formula_weight         1299.59
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-10-26
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_audit_update_record
;
2021-12-26 deposited with the CCDC.	2022-03-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.590(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.4250(2)
_cell_length_b                   26.1150(5)
_cell_length_c                   17.3913(4)
_cell_measurement_reflns_used    15382
_cell_measurement_temperature    229.99(12)
_cell_measurement_theta_max      79.1450
_cell_measurement_theta_min      3.3800
_cell_volume                     5348.67(19)
_computing_cell_refinement       'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (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      229.99(12)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.979
_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    -68.00  27.00   0.50    4.00    --  -46.88  70.00  96.00  190
  2  \w    -97.00 -72.00   0.50    4.00    --  -46.88 -70.00 -35.00   50
  3  \w     50.00 106.00   0.50    4.00    --   46.88  70.00  96.00  112
  4  \w    -24.00  59.00   0.50    4.00    --   46.88 -70.00 -35.00  166
  5  \w    -82.00 -57.00   0.50   25.00    --  -91.75  70.00  96.00   50
  6  \w   -143.00-117.00   0.50   25.00    --  -91.75 -70.00 -35.00   52
  7  \w     93.00 173.00   0.50   25.00    --  113.25  70.00  96.00  160
  8  \w     41.00  71.00   0.50   25.00    --  113.25 -70.00 -35.00   60
  9  \w   -120.00 -78.00   0.50    4.00    --  -46.88-125.00 120.00   84
 10  \w   -118.00 -79.00   0.50    4.00    --  -46.88-125.00  90.00   78
 11  \w    -44.00 -16.00   0.50   25.00    --  -91.75  30.00 -90.00   56
 12  \w    -59.00 -24.00   0.50   25.00    --  -91.75  45.00 -60.00   70
 13  \w    140.00 177.00   0.50   25.00    --  113.25  77.00  30.00   74
 14  \w     43.00  95.00   0.50   25.00    --  113.25 -77.00   0.00  104
 15  \w    132.00 172.00   0.50   25.00    --  113.25  15.00  30.00   80
 16  \w    143.00 172.00   0.50   25.00    --  113.25  61.00  60.00   58
 17  \w     90.00 128.00   0.50   25.00    --  113.25  77.00  30.00   76
 18  \w     51.00  79.00   0.50   25.00    --  113.25 -94.00-180.00   56
 19  \w    133.00 160.00   0.50   25.00    --  113.25  45.00-180.00   54
 20  \w     42.00 107.00   0.50   25.00    --  113.25 -94.00-120.00  130
 21  \w     44.00  87.00   0.50   25.00    --  113.25-125.00 120.00   86
 22  \w     43.00  73.00   0.50   25.00    --  113.25-125.00 -30.00   60
 23  \w     41.00  70.00   0.50   25.00    --  113.25 -77.00 120.00   58
 24  \w    111.00 139.00   0.50   25.00    --  113.25  61.00  60.00   56
 25  \w    100.00 168.00   0.50   25.00    --  113.25  45.00  30.00  136
 26  \w     70.00  96.00   0.50   25.00    --  113.25 -77.00 -30.00   52
 27  \w    100.00 171.00   0.50   25.00    --  113.25  45.00-150.00  142
 28  \w    112.00 160.00   0.50   25.00    --  113.25  61.00 -60.00   96
 29  \w     59.00  84.00   0.50   25.00    --  113.25 -77.00  30.00   50
 30  \w    102.00 131.00   0.50   25.00    --  113.25  45.00-180.00   58
 31  \w     78.00 107.00   0.50   25.00    --  113.25-125.00 -30.00   58
 32  \w     42.00  96.00   0.50   25.00    --  113.25 -77.00 -90.00  108
 33  \w     47.00  73.00   0.50   25.00    --  113.25 -77.00-150.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0892903000
_diffrn_orient_matrix_UB_12      -0.0400447000
_diffrn_orient_matrix_UB_13      -0.0036276000
_diffrn_orient_matrix_UB_21      -0.0845202000
_diffrn_orient_matrix_UB_22      -0.0228615000
_diffrn_orient_matrix_UB_23      -0.0774653000
_diffrn_orient_matrix_UB_31      0.0446303000
_diffrn_orient_matrix_UB_32      0.0368048000
_diffrn_orient_matrix_UB_33      -0.0521592000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0471
_diffrn_reflns_av_unetI/netI     0.0443
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            48200
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.533
_diffrn_reflns_theta_min         3.170
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.068
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74652
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.118a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark purple'
_exptl_crystal_density_diffrn    1.614
_exptl_crystal_description       plate
_exptl_crystal_F_000             2592
_exptl_crystal_size_max          0.04
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.725
_refine_diff_density_min         -1.196
_refine_diff_density_rms         0.105
_refine_ls_extinction_coef       0.00020(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     692
_refine_ls_number_reflns         11477
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.083
_refine_ls_R_factor_all          0.0959
_refine_ls_R_factor_gt           0.0746
_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^)+(0.0725P)^2^+21.8803P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1771
_refine_ls_wR_factor_ref         0.1890
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8498
_reflns_number_total             11477
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00675h2.cif
_cod_data_source_block           str0758lt230kcu34mm_auto
_cod_database_code               7709785
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C46 H34 N4 O2 F6 P Sb'
_shelx_estimated_absorpt_t_max   0.839
_shelx_estimated_absorpt_t_min   0.713
_reflns_odcompleteness_completeness 99.62
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C26-Cl7 = C26-Cl8 = C26-Cl9
 1.8 with sigma of 0.01
 Cl7-Cl9
 2.7 with sigma of 0.01
 C27-Cl7A = C27-Cl8A = C27-Cl9A
 1.8 with sigma of 0.01
 Cl7A-Cl9A
 2.7 with sigma of 0.01
3. Others
 Sof(Cl7A)=Sof(Cl8A)=Sof(C27)=Sof(H27)=Sof(Cl9A)=1-FVAR(1)
 Sof(Cl8)=Sof(Cl7)=Sof(C26)=Sof(H26)=Sof(Cl9)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C24(H24), C25(H25), C26(H26), C27(H27)
4.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C8(H8), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C2A(H2A), C3A(H3A),
  C7A(H7A), C8A(H8A), C12A(H12A), C13A(H13A), C14A(H14A), C15A(H15A),
 C16A(H16A), C18A(H18A), C19A(H19A), C20A(H20A), C21A(H21A), C22A(H22A)
4.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C23A(H23D,H23E,H23F)
;
_shelx_res_checksum              58538
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 3.219
_oxdiff_exptl_absorpt_empirical_full_min 0.416