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_7709787
_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         'C58 H58 N4 O14 Sb, 2(C H Cl3), F6 P'
_chemical_formula_sum            'C60 H60 Cl6 F6 N4 O14 P Sb'
_chemical_formula_weight         1540.54
_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
_audit_creation_date             2022-03-16
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_audit_update_record
;
2022-03-18 deposited with the CCDC.	2022-03-21 downloaded from the CCDC.
;
_cell_angle_alpha                104.0630(11)
_cell_angle_beta                 103.8304(11)
_cell_angle_gamma                102.0038(12)
_cell_formula_units_Z            1
_cell_length_a                   8.52553(12)
_cell_length_b                   14.3097(2)
_cell_length_c                   14.55804(17)
_cell_measurement_reflns_used    18170
_cell_measurement_temperature    229.99(11)
_cell_measurement_theta_max      79.6470
_cell_measurement_theta_min      3.2900
_cell_volume                     1604.74(4)
_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(11)
_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   -119.00 -63.00   0.50    0.50    --  -46.88 -18.00  -8.00  112
  2  \w     33.00 123.00   0.50    0.50    --   46.88  18.00 159.00  180
  3  \w    -20.00  16.00   0.50    0.50    --   46.88 -18.00  -8.00   72
  4  \w   -108.00 -82.00   0.50    2.50    --  -91.75 -18.00  -8.00   52
  5  \w   -159.00-121.00   0.50    2.50    --  -91.75 -18.00  -8.00   76
  6  \w    108.00 165.00   0.50    2.50    --  113.25  18.00 159.00  114
  7  \w   -120.00 -95.00   0.50    0.50    --  -46.88 -77.00-150.00   50
  8  \w    -30.00  29.00   0.50    0.50    --  -46.88  18.00 159.00  118
  9  \w     37.00  94.00   0.50    0.50    --   46.88-125.00-150.00  114
 10  \w      9.00  53.00   0.50    0.50    --   46.88 -57.00-180.00   88
 11  \w    -23.00  69.00   0.50    0.50    --   46.88 -77.00   0.00  184
 12  \w    -61.00 -23.00   0.50    2.50    --  -91.75  45.00 120.00   76
 13  \w    -57.00 -31.00   0.50    2.50    --  -91.75  45.00 150.00   52
 14  \w    -45.00 -17.00   0.50    2.50    --  -91.75  30.00 -30.00   56
 15  \w    -86.00 -29.00   0.50    2.50    --  -91.75 125.00-150.00  114
 16  \w    104.00 166.00   0.50    2.50    --  113.25  45.00  60.00  124
 17  \w     65.00 109.00   0.50    2.50    --  113.25-125.00 -90.00   88
 18  \w     83.00 112.00   0.50    2.50    --  113.25-125.00 -30.00   58
 19  \w    100.00 153.00   0.50    2.50    --  113.25  45.00 -90.00  106
 20  \w     43.00  72.00   0.50    2.50    --  113.25 -77.00  90.00   58
 21  \w     42.00  90.00   0.50    2.50    --  113.25 -77.00 150.00   96
 22  \w     44.00  70.00   0.50    2.50    --  113.25 -94.00  90.00   52
 23  \w     48.00  93.00   0.50    2.50    --  113.25 -77.00-120.00   90
 24  \w     63.00 107.00   0.50    2.50    --  113.25 -94.00  60.00   88
 25  \w     44.00  83.00   0.50    2.50    --  113.25 -94.00 150.00   78
 26  \w    104.00 158.00   0.50    2.50    --  113.25  45.00-150.00  108
 27  \w     48.00  88.00   0.50    2.50    --  113.25 -77.00  30.00   80
 28  \w     54.00  80.00   0.50    2.50    --  113.25-125.00 -30.00   52
 29  \w     41.00  91.00   0.50    2.50    --  113.25 -77.00 -60.00  100
 30  \w    101.00 172.00   0.50    2.50    --  113.25  15.00 120.00  142
 31  \w     67.00 111.00   0.50    2.50    --  113.25-125.00-120.00   88
 32  \w     74.00 112.00   0.50    2.50    --  113.25-125.00   0.00   76
 33  \w    101.00 161.00   0.50    2.50    --  113.25  61.00-180.00  120
 34  \w    101.00 128.00   0.50    2.50    --  113.25  61.00   0.00   54
 35  \w    134.00 175.00   0.50    2.50    --  113.25  61.00   0.00   82
 36  \w     59.00 101.00   0.50    2.50    --  113.25 -94.00  30.00   84
 37  \w    103.00 177.00   0.50    2.50    --  113.25  30.00 -60.00  148
 38  \w     43.00 112.00   0.50    2.50    --  113.25-125.00  60.00  138
 39  \w     80.00 111.00   0.50    2.50    --  113.25-125.00-150.00   62
 40  \w     48.00  73.00   0.50    2.50    --  113.25-125.00-150.00   50
 41  \w    108.00 136.00   0.50    2.50    --  113.25  45.00 -30.00   56
 42  \w    147.00 178.00   0.50    2.50    --  113.25  45.00 -30.00   62
 43  \w     60.00  85.00   0.50    2.50    --  113.25 -94.00-120.00   50
 44  \w     61.00 112.00   0.50    2.50    --  113.25-125.00-180.00  102
 45  \w     90.00 143.00   0.50    2.50    --  113.25  77.00-150.00  106
 46  \w     79.00 107.00   0.50    2.50    --  113.25 -94.00 -90.00   56
 47  \w     45.00  90.00   0.50    2.50    --  113.25 -94.00 120.00   90
 48  \w     48.00  73.00   0.50    2.50    --  113.25 -77.00 -90.00   50
 49  \w     42.00 111.00   0.50    2.50    --  113.25-125.00  30.00  138
 50  \w     82.00 107.00   0.50    2.50    --  113.25 -94.00-180.00   50
 51  \w     45.00  70.00   0.50    2.50    --  113.25-125.00 120.00   50
 52  \w     87.00 112.00   0.50    2.50    --  113.25-125.00 120.00   50
 53  \w     79.00 104.00   0.50    2.50    --  113.25 -94.00  90.00   50
;
_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      0.1392769000
_diffrn_orient_matrix_UB_12      0.0918708000
_diffrn_orient_matrix_UB_13      0.0072068000
_diffrn_orient_matrix_UB_21      0.1335669000
_diffrn_orient_matrix_UB_22      -0.0548835000
_diffrn_orient_matrix_UB_23      0.0267011000
_diffrn_orient_matrix_UB_31      -0.0199035000
_diffrn_orient_matrix_UB_32      -0.0439690000
_diffrn_orient_matrix_UB_33      -0.1111690000
_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  0.0529
_diffrn_reflns_av_unetI/netI     0.0402
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            24477
_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         80.114
_diffrn_reflns_theta_min         3.286
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.680
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65434
_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            'clear light green'
_exptl_crystal_density_diffrn    1.594
_exptl_crystal_description       plate
_exptl_crystal_F_000             782
_exptl_crystal_size_max          0.045
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.337
_refine_diff_density_min         -1.446
_refine_diff_density_rms         0.114
_refine_ls_extinction_coef       0.0016(3)
_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   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     429
_refine_ls_number_reflns         6858
_refine_ls_number_restraints     90
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0623
_refine_ls_R_factor_gt           0.0618
_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^)+(0.1061P)^2^+2.9743P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1642
_refine_ls_wR_factor_ref         0.1647
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6785
_reflns_number_total             6858
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00675h2.cif
_cod_data_source_block           str0757lt230kcu34mm_auto
_cod_database_code               7709787
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C58 H58 N4 O14 F6 P Sb'
_shelx_estimated_absorpt_t_max   0.878
_shelx_estimated_absorpt_t_min   0.753
_reflns_odcompleteness_completeness 99.68
_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
 O6A-C28A
 1.45 with sigma of 0.02
 C30A-Cl2A
 1.8 with sigma of 0.01
 C30A-Cl3A
 1.8 with sigma of 0.01
 C30A-Cl1A
 1.8 with sigma of 0.01
 C29A-O7
 1.37 with sigma of 0.01
 Cl3A-Cl1A
 2.7 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C30 \\sim Cl1 \\sim Cl2 \\sim Cl3: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
O7 \\sim C29: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C30A \\sim Cl1A \\sim Cl2A \\sim Cl3A: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01 within 2A
O7 \\sim C29A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
Uanis(O5) = Uanis(O5A)
Uanis(C17) = Uanis(C18) = Uanis(C19) = Uanis(C20) = Uanis(C21) = Uanis(C22)
Uanis(C17A) = Uanis(C18A) = Uanis(C19A) = Uanis(C20A) = Uanis(C21A) =
Uanis(C22A) = Uanis(C28A)
Uanis(C26) = Uanis(C27) = Uanis(C28)
Uanis(C30) = Uanis(C30A)
Uanis(Cl3) = Uanis(Cl1A) = Uanis(Cl1) = Uanis(Cl2A) = Uanis(Cl2) = Uanis(Cl3A)
Uanis(C29) = Uanis(C29A)
Uanis(C27A) = Uanis(C28A)
4. Rigid body (RIGU) restrains
 C30A, Cl1A, Cl2A, Cl3A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 O7, C29
 with sigma for 1-2 distances of 0.05 and sigma for 1-3 distances of 0.05
 C30, Cl1, Cl3, Cl2
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 O7, C29A
 with sigma for 1-2 distances of 0.05 and sigma for 1-3 distances of 0.05
5. Others
 Sof(Cl3A)=Sof(Cl1A)=Sof(C30A)=Sof(H30A)=Sof(Cl2A)=Sof(C29A)=Sof(H29D)=
 Sof(H29E)=Sof(H29F)=1-FVAR(1)
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=Sof(C30)=
 Sof(H30)=FVAR(1)
 Sof(O6A)=Sof(C17A)=Sof(C22A)=Sof(H22A)=Sof(C21A)=Sof(C20A)=Sof(C19A)=
 Sof(C18A)=Sof(H18A)=Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(O5A)=Sof(C27A)=
 Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(O4A)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=
 1-FVAR(2)
 Sof(O4)=Sof(O5)=Sof(O6)=Sof(C17)=Sof(C18)=Sof(H18)=Sof(C19)=Sof(C20)=Sof(C21)=
 Sof(C22)=Sof(H22)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C28)=Sof(H28A)=
 Sof(H28B)=Sof(H28C)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C30(H30), C30A(H30A)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C7(H7), C8(H8), C12(H12), C16(H16), C18(H18), C22(H22),
 C22A(H22A), C18A(H18A)
6.c Fitted hexagon refined as free rotating group:
 C17(C18,C19,C20,C21,C22), C17A(C22A,C21A,C20A,C19A,C18A)
6.d Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C27(H27A,H27B,H27C),
 C28A(H28D,H28E,H28F), C27A(H27D,H27E,H27F), C26A(H26D,H26E,H26F), C29A(H29D,
 H29E,H29F)
;
_shelx_res_checksum              74958
_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 1.553
_oxdiff_exptl_absorpt_empirical_full_min 0.046