The influence of charge transfer on the emissive properties of pyridine dipyrrolide bismuth complexes.
Deuter, Katharina L.; Vollmar, Katharina; Rieser, Jan; Linseis, Michael; Winter, Rainer F.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 9921–9929; doi:10.1039/d5dt00869g

data_7718844
_publ_section_title
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 The influence of charge transfer on the emissive properties of pyridine
 dipyrrolide bismuth complexes.
;
_journal_issue                   25
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9921
_journal_page_last               9929
_journal_paper_doi               10.1039/d5dt00869g
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         '2(C41 H27 Bi Br F6 N3 O2), 0.5[C6H14]'
_chemical_formula_sum            'C83 H56 Bi2 Br2 F12 N6 O4.25'
_chemical_formula_weight         2011.156
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_Int_Tables_number      2
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-02-10
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-04-09 deposited with the CCDC.	2025-05-28 downloaded from the CCDC.
;
_cell_angle_alpha                95.724(3)
_cell_angle_beta                 110.728(3)
_cell_angle_gamma                104.280(3)
_cell_formula_units_Z            2
_cell_length_a                   13.4323(5)
_cell_length_b                   16.9364(6)
_cell_length_c                   17.9664(6)
_cell_measurement_reflns_used    50268
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.07
_cell_measurement_theta_min      1.93
_cell_volume                     3624.8(3)
_computing_cell_refinement
;
X-Area Recipe 1.33.0.0 (STOE, 2015)
;
_computing_data_collection
;
X-Area WinXpose 2.0.22.0 (STOE, 2016)
;
_computing_data_reduction
;
X-Area Integrate 1.74.2.0 (STOE, 2018)
X-Area LANA 1.75.3.0 (STOE, 2018)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5 (Bourhis et al., 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'image plate (34 cm diameter)'
_diffrn_detector_area_resol_mean 6.67
_diffrn_detector_type            'STOE Imaging Plate'
_diffrn_measured_fraction_theta_full 0.9947
_diffrn_measured_fraction_theta_max 0.9815
_diffrn_measurement_details
;
 420 frames, detector distance = 80 mm
;
_diffrn_measurement_device       '2-circle diffractometer'
_diffrn_measurement_device_type  'STOE IPDS 2T'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '0.5 mm diameter, monocapillary'
_diffrn_radiation_monochromator  'plane graphite'
_diffrn_radiation_polarisn_norm  0
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0793
_diffrn_reflns_av_unetI/netI     0.0765
_diffrn_reflns_Laue_measured_fraction_full 0.9947
_diffrn_reflns_Laue_measured_fraction_max 0.9815
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            30648
_diffrn_reflns_point_group_measured_fraction_full 0.9947
_diffrn_reflns_point_group_measured_fraction_max 0.9815
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         27.64
_diffrn_reflns_theta_min         2.25
_diffrn_source
'Sealed Mo X-ray tube, 12 x 0.4 mm long-fine focus'
_diffrn_source_current           40
_diffrn_source_power             2.000
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    6.039
_exptl_absorpt_correction_T_max  0.1224
_exptl_absorpt_correction_T_min  0.0265
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens, "The Evaluation of Absorption and Extinction in Single-Crystal
Structure Analysis", published in: F. R. Ahmed (Editor), "Crystallographic
Computing", Munksgaard, Copenhagen (1970), 255 - 270.
Afterwards scaling of reflection intensities was performed within STOE LANA.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(\m~2~-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
Finally a spherical absorption correction was done within STOE LANA.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.843
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       platelet
_exptl_crystal_F_000             1934.655
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.173
_exptl_crystal_size_min          0.02
_refine_diff_density_max         7.5649
_refine_diff_density_min         -8.0544
_refine_diff_density_rms         0.4495
_refine_ls_d_res_high            0.7660
_refine_ls_d_res_low             9.0710
_refine_ls_goodness_of_fit_ref   1.1953
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    112
_refine_ls_number_parameters     1022
_refine_ls_number_reflns         16587
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      1.1924
_refine_ls_R_factor_all          0.1244
_refine_ls_R_factor_gt           0.1003
_refine_ls_shift/su_max          -0.0008
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2726
_refine_ls_wR_factor_ref         0.3018
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              16
_reflns_limit_h_min              -17
_reflns_limit_k_max              21
_reflns_limit_k_min              -21
_reflns_limit_l_max              23
_reflns_limit_l_min              0
_reflns_number_gt                12493
_reflns_number_total             16587
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5dt00869g2.cif
_cod_data_source_block           JRKD10-THF-hex
_cod_depositor_comments
'Adding full bibliography for 7718839--7718844.cif.'
_cod_database_code               7718844
_olex2_refinement_description
;
1. Restrained distances
 O5-C83 = O5-C86
 1.44 with sigma of 0.02
 C83-C84 = C85-C86
 1.53 with sigma of 0.02
 C84-C85
 1.54 with sigma of 0.02
 O5-C84 = O5-C85 = C83-C85 = C84-C86
 2.38 with sigma of 0.04
 O5-C83 \\sim O5-C86
 with sigma of 0.02
 O5-C84 \\sim O5-C85
 with sigma of 0.04
 C83-C84 \\sim C84-C85 \\sim C85-C86
 with sigma of 0.02
 C84-C86 \\sim C83-C85
 with sigma of 0.04
2. Uiso/Uaniso restraints and constraints
O5 \\sim C83 \\sim C84 \\sim C85 \\sim C86: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
3. Rigid body (RIGU) restrains
 O5, C83, C86, C84, C85
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Fixed Sof: O5(0.25) C83(0.25) H3a(0.25) H3b(0.25) C84(0.25) H4a(0.25)
 H4b(0.25) C85(0.25) H5a(0.25) H5b(0.25) C86(0.25) H6a(0.25) H6b(0.25)
5.a Secondary CH2 refined with riding coordinates:
 C83(H3a,H3b), C84(H4a,H4b), C85(H5a,H5b), C86(H6a,H6b)
5.b Aromatic/amide H refined with riding coordinates:
 C22(H00O), C63(H00Q), C1(H00S), C61(H00T), C40(H00U), C26(H00X), C33(H00Y),
 C43(H011), C54(H019), C78(H01D), C67(H01G), C29(H01H), C42(H01I), C36(H01K),
 C47(H01L), C39(H01M), C2(H01P), C37(H01Q), C58(H01R), C60(H01S), C30(H01T),
 C57(H01U), C80(H01Z), C77(H020), C19(H022), C81(H023), C20(H025), C32(H027),
 C6(H028), C53(H029), C70(H02C), C9(H02D), C12(H02E), C73(H02F), C50(H02G),
 C16(H02H), C74(H02I), C13(H02K), C17(H02M), C51(H02O), C10(H02V), C71(H02W)
5.c Idealised Me refined as rotating group:
 C34(H02a,H02b,H02j), C14(H02l,H02n,H02p), C55(H02q,H02r,H02s), C75(H03a,H03b,
 H03c)
;
_olex2_refine_details
;
Refinement using NoSpherA2, an implementation of
NOn-SPHERical Atom-form-factors in Olex2.
Please cite:
F. Kleemiss et al. Chem. Sci. DOI 10.1039/D0SC05526C - 2021
NoSpherA2 implementation of HAR makes use of
tailor-made aspherical atomic form factors calculated
on-the-fly from a Hirshfeld-partitioned electron density (ED) - not from
spherical-atom form factors.

The ED is calculated from a gaussian basis set single determinant SCF
wavefunction - either Hartree-Fock or DFT using selected funtionals
 - for a fragment of the crystal.
This fragment can be embedded in an electrostatic crystal field by employing cluster charges
or modelled using implicit solvation models, depending on the software used.
The following options were used:
   SOFTWARE:       ORCA 5.0
   PARTITIONING:   NoSpherA2
   INT ACCURACY:   Normal
   METHOD:         R2SCAN
   BASIS SET:      x2c-TZVP
   CHARGE:         0
   MULTIPLICITY:   1
   RELATIVISTIC:   DKH2
   DATE:           2025-02-05_12-17-11
;
_olex2_submission_special_instructions 'No special instructions were received'