Difluorenoheteroles: topological control of π conjugation in diradicaloids and mixed-valence radical ions
Prajapati, Bibek; Kwenda, Tendai; Lis, Tadeusz; Chmielewski, Piotr J.; Gómez-García, Carlos J.; Majewski, Marcin A.; Stępień, Marcin; Chemical Science 15 (2024) 10101–10109; doi:10.1039/D4SC02459A

data_1571707
_publ_section_title
;
 Difluorenoheteroles: topological control of \p conjugation in
 diradicaloids and mixed-valence radical ions
;
_journal_issue                   26
_journal_name_full               'Chemical Science'
_journal_page_first              10101
_journal_page_last               10109
_journal_paper_doi               10.1039/D4SC02459A
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C56 H58 S, 1.5(C7 D8)'
_chemical_formula_sum            'C66.5 H58 D12 S'
_chemical_formula_weight         913.35
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_method           SHELXL-2013
_audit_update_record
;
2023-10-22 deposited with the CCDC.	2024-05-21 downloaded from the CCDC.
;
_cell_angle_alpha                104.66(2)
_cell_angle_beta                 97.26(2)
_cell_angle_gamma                102.40(2)
_cell_formula_units_Z            2
_cell_length_a                   9.2015(19)
_cell_length_b                   15.281(4)
_cell_length_c                   20.007(3)
_cell_measurement_reflns_used    19930
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      60
_cell_measurement_theta_min      2.3
_cell_volume                     2609.0(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.952
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_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  0.0552
_diffrn_reflns_av_unetI/netI     0.0388
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            39794
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        67.000
_diffrn_reflns_theta_max         73.983
_diffrn_reflns_theta_min         2.326
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.843
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.741
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light pink'
_exptl_crystal_density_diffrn    1.163
_exptl_crystal_description       plate
_exptl_crystal_F_000             970
_exptl_crystal_size_max          0.390
_exptl_crystal_size_mid          0.040
_exptl_crystal_size_min          0.020
_refine_diff_density_max         0.603
_refine_diff_density_min         -0.547
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     665
_refine_ls_number_reflns         10083
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0666
_refine_ls_R_factor_gt           0.0575
_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^)+(0.1161P)^2^+0.3112P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1654
_refine_ls_wR_factor_ref         0.1725
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8290
_reflns_number_total             10083
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02459a3.cif
_cod_data_source_block           tw19ca
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_atom_sites_solution_primary' value 'direct methods' was
changed to 'direct'.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1571707--1571709.cif.
;
_cod_original_formula_sum        'C66.50 H58 D12 S'
_cod_database_code               1571707
_shelxl_version_number           2013-2
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.735
_olex2_refinement_description
;
1. Others
 Fixed Sof: D1C(0.5) C7C(0.5) D7CA(0.5) D7CB(0.5) D7CC(0.5) C1D(0.5) C2D(0.5)
 D2D(0.5) C3D(0.5) D3D(0.5) C4D(0.5) D4D(0.5) C5D(0.5) D5D(0.5) C6D(0.5)
 D6D(0.5) C7D(0.5) D7DA(0.5) D7DB(0.5) D7DC(0.5) C1E(0.5) C2E(0.5) D2E(0.5)
 C3E(0.5) D3E(0.5) C4E(0.5) D4E(0.5) C5E(0.5) D5E(0.5) C6E(0.5) D6E(0.5)
 C7E(0.5) D7EA(0.5) D7EB(0.5) D7EC(0.5)
 Fixed Uiso: H3A(0.029) H6(0.029) H8A(0.036) H9A(0.044) H10A(0.045) H11A(0.04)
 H16A(0.036) H18A(0.038) H20A(0.035) H21A(0.051) H21B(0.051) H21C(0.051)
 H22A(0.056) H22B(0.056) H22C(0.056) H25(0.042) H24A(0.058) H24B(0.058)
 H24C(0.058) H25A(0.069) H25B(0.069) H25C(0.069) H26A(0.043) H27A(0.065)
 H27B(0.065) H27C(0.065) H28A(0.068) H28B(0.068) H28C(0.068) H3B(0.029)
 H6B(0.03) H8B(0.034) H9B(0.038) H10B(0.04) H11B(0.035) H16B(0.031) H18B(0.032)
 H20B(0.038) H21D(0.06) H21E(0.06) H21F(0.06) H22D(0.069) H22E(0.069)
 H22F(0.069) H23B(0.034) H24D(0.053) H24E(0.053) H24F(0.053) H25D(0.054)
 H25E(0.054) H25F(0.054) H26B(0.042) H27D(0.071) H27E(0.071) H27F(0.071)
 H28D(0.077) H28E(0.077) H28F(0.077) D1C(0.063) D2C(0.057) D3C(0.061)
 D7CA(0.098) D7CB(0.098) D7CC(0.098) D2D(0.071) D3D(0.141) D4D(0.175)
 D5D(0.134) D6D(0.107) D7DA(0.135) D7DB(0.135) D7DC(0.135) D2E(0.094)
 D3E(0.129) D4E(0.083) D5E(0.085) D6E(0.071) D7EA(0.163) D7EB(0.163) D7EC(0.163)
 Fixed X: H3A(0.4045) H6(0.478) H8A(0.1861) H9A(-0.0011) H10A(-0.0714)
 H11A(0.0424) H16A(0.439) H18A(0.1286) H20A(0.403) H21A(0.6643) H21B(0.6717)
 H21C(0.613) H22A(0.3443) H22B(0.4977) H22C(0.5049) H25(0.2175) H24A(0.538)
 H24B(0.4487) H24C(0.4581) H25A(0.2989) H25B(0.206) H25C(0.3873) H26A(0.0877)
 H27A(-0.1215) H27B(-0.1671) H27C(-0.1063) H28A(0.1885) H28B(0.0139)
 H28C(0.062) H3B(0.5648) H6B(0.851) H8B(0.6432) H9B(0.7444) H10B(0.9109)
 H11B(0.9848) H16B(1.0024) H18B(1.3423) H20B(0.7292) H21D(0.8235) H21E(0.6504)
 H21F(0.7813) H22D(0.7223) H22E(0.5763) H22F(0.6951) H23B(1.2946) H24D(1.222)
 H24E(1.2878) H24F(1.1213) H25D(1.4986) H25E(1.5131) H25F(1.4548) H26B(1.1244)
 H27D(1.4288) H27E(1.3706) H27F(1.3194) H28D(1.152) H28E(1.2749) H28F(1.324)
 D1C(0.7582) D2C(0.8071) D3C(0.9561) D7CA(0.6374) D7CB(0.7009) D7CC(0.6549)
 D2D(0.879) D3D(0.6942) D4D(0.6762) D5D(0.843) D6D(1.0279) D7DA(1.1591)
 D7DB(1.1372) D7DC(1.034) D2E(0.851) D3E(0.6484) D4E(0.5937) D5E(0.7416)
 D6E(0.9442) D7EA(1.0859) D7EB(1.0121) D7EC(1.1272)
 Fixed Y: H3A(0.1933) H6(0.5044) H8A(0.1674) H9A(0.1819) H10A(0.3211)
 H11A(0.4506) H16A(0.7628) H18A(0.6897) H20A(0.5269) H21A(0.6614) H21B(0.5825)
 H21C(0.5533) H22A(0.6476) H22B(0.6248) H22C(0.716) H25(0.849) H24A(0.882)
 H24B(0.8518) H24C(0.9526) H25A(0.969) H25B(0.8781) H25C(0.9078) H26A(0.4411)
 H27A(0.556) H27B(0.4458) H27C(0.4842) H28A(0.5183) H28B(0.4648) H28C(0.5758)
 H3B(0.1087) H6B(0.3014) H8B(-0.0578) H9B(-0.1857) H10B(-0.1816) H11B(-0.048)
 H16B(0.1669) H18B(0.2637) H20B(0.0539) H21D(-0.0196) H21E(-0.0167)
 H21F(0.0562) H22D(0.1975) H22E(0.1305) H22F(0.2058) H23B(0.2056) H24D(0.3819)
 H24E(0.3455) H24F(0.294) H25D(0.2665) H25E(0.3295) H25F(0.3645) H26B(0.1695)
 H27D(0.2066) H27E(0.1656) H27F(0.1034) H28D(0.3321) H28E(0.3115) H28F(0.3464)
 D1C(0.4351) D2C(0.5738) D3C(0.3621) D7CA(0.3848) D7CB(0.3835) D7CC(0.4742)
 D2D(-0.0073) D3D(0.048) D4D(0.2012) D5D(0.299) D6D(0.2437) D7DA(0.1306)
 D7DB(0.0445) D7DC(0.035) D2E(-0.0127) D3E(0.0137) D4E(0.1598) D5E(0.2794)
 D6E(0.2529) D7EA(0.0563) D7EB(0.0928) D7EC(0.1657)
 Fixed Z: H3A(0.1101) H6(0.2585) H8A(-0.0061) H9A(-0.0912) H10A(-0.0788)
 H11A(0.0198) H16A(0.157) H18A(0.2714) H20A(0.0536) H21A(0.1433) H21B(0.0748)
 H21C(0.1399) H22A(0.0089) H22B(-0.0113) H22C(0.051) H25(0.2834) H24A(0.2914)
 H24B(0.349) H24C(0.3374) H25A(0.2343) H25B(0.172) H25C(0.1854) H26A(0.2049)
 H27A(0.2132) H27B(0.2037) H27C(0.1423) H28A(0.3249) H28B(0.3146) H28C(0.3282)
 H3B(0.1649) H6B(0.39) H8B(0.1376) H9B(0.1406) H10B(0.2402) H11B(0.3384)
 H16B(0.5829) H18B(0.4906) H20B(0.4235) H21D(0.5074) H21E(0.5063) H21F(0.5679)
 H22D(0.5457) H22E(0.4896) H22F(0.4672) H23B(0.6395) H24D(0.6569) H24E(0.7197)
 H24F(0.6742) H25D(0.5905) H25E(0.6694) H25F(0.6044) H26B(0.3142) H27D(0.3869)
 H27E(0.3035) H27F(0.354) H28D(0.3573) H28E(0.3097) H28F(0.3936) D1C(0.5178)
 D2C(0.4855) D3C(0.5333) D7CA(0.4731) D7CB(0.551) D7CC(0.5387) D2D(0.0351) D3D(-
 0.0208) D4D(0.0259) D5D(0.1286) D6D(0.1846) D7DA(0.1877) D7DB(0.119)
 D7DC(0.1768) D2E(0.027) D3E(-0.0414) D4E(-0.012) D5E(0.086) D6E(0.1544)
 D7EA(0.1195) D7EB(0.1861) D7EC(0.16)
;
_shelx_res_checksum              98167
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.801
_oxdiff_exptl_absorpt_empirical_full_min 0.655