Persistent, highly localized, and tunable [4]helicene radicals
Shaikh, Aslam C.; Moutet, Jules; Veleta, José M.; Hossain, Md Mubarak; Bloch, Jan; Astashkin, Andrei V.; Gianetti, Thomas L.; Chemical Science  (2020) –; doi:10.1039/D0SC04850J

data_1559173
_publ_section_title
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 Persistent, highly localized, and tunable [4]helicene radicals
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_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC04850J
_journal_year                    2020
_chemical_formula_moiety         'C30.95 H38.88 N4 O2, 0.33(H2 O)'
_chemical_formula_sum            'C30.95 H39.55 N4 O2.33'
_chemical_formula_weight         505.00
_chemical_name_common            2-Hradical
_chemical_name_systematic        2-Hradical
_chemical_properties_physical    Air-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-10-30
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-05-20 deposited with the CCDC.	2020-09-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   20.1829(5)
_cell_length_b                   10.7314(3)
_cell_length_c                   25.5707(7)
_cell_measurement_reflns_used    9884
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      73.08
_cell_measurement_theta_min      3.56
_cell_volume                     5538.4(3)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.857
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34138
_diffrn_reflns_av_R_equivalents  0.0549
_diffrn_reflns_av_unetI/netI     0.0405
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.857
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            45766
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.857
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         73.269
_diffrn_reflns_theta_min         3.560
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.391
_exptl_absorpt_correction_T_max  0.7537
_exptl_absorpt_correction_T_min  0.6302
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1038 before and 0.0593 after correction. The Ratio of minimum to maximum transmission is 0.8361. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'metallic dark violet'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.211
_exptl_crystal_description       needle
_exptl_crystal_F_000             2176
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene/hexanes'
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.535
_refine_diff_density_min         -0.246
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     414
_refine_ls_number_reflns         7238
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.109
_refine_ls_R_factor_all          0.0906
_refine_ls_R_factor_gt           0.0669
_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^)+(0.0528P)^2^+3.1410P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1402
_refine_ls_wR_factor_ref         0.1505
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5594
_reflns_number_total             7238
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc04850j2.cif
_cod_data_source_block           2-Hradical
_cod_database_code               1559173
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.955
_olex2_refinement_description
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1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C3AA-N0AB
 1.47 with sigma of 0.01
 N0AA-C4 \\sim N0AB-C1AA
 with sigma of 0.02
 N0AA-C6 \\sim N0AB-C6A
 with sigma of 0.02
 C3-C4 \\sim C4AA-C1AA
 with sigma of 0.02
 N0AA-C3 \\sim N0AB-C4AA
 with sigma of 0.04
 C4-C6 \\sim C1AA-C6A
 with sigma of 0.04
3. Others
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=1-FVAR(1)
 Fixed Sof: N0AA(0.6667) C3(0.6667) H3A(0.6667) H3B(0.6667) C4(0.6667)
 H4A(0.6667) C6(0.6667) H6A(0.6667) H6B(0.6667) H6C(0.6667) C4AA(0.33333)
 H4AD(0.33333) H4AE(0.33333) C1AA(0.33333) H1AA(0.33333) H1AB(0.33333)
 N0AB(0.33333) C6A(0.33333) H6AA(0.33333) H6AB(0.33333) H6AC(0.33333)
 O2A(0.33333) H2AA(0.33333) H2AB(0.33333) H3AC(0.6667) H3AD(0.6667)
 H3AE(0.6667) H3AF(0.33333) H3AG(0.33333) H3AH(0.33333) H4B(0.6667)
 C0AA(0.33333) H0AA(0.33333) H0AB(0.33333) C2(0.6667) H2A(0.6667) H2B(0.6667)
4.a Free rotating group:
 O2A(H2AA,H2AB)
4.b Secondary CH2 refined with riding coordinates:
 C00I(H00C,H00E), C3A(H3AA,H3AB), C3(H3A,H3B), C4AA(H4AD,H4AE), C1AA(H1AA,
 H1AB), C0AA(H0AA,H0AB), C2(H2A,H2B)
4.c Aromatic/amide H refined with riding coordinates:
 C00A(H00A), C00B(H00B), C00D(H00D), C00L(H00L), C00M(H00M), C00N(H00N),
 C00O(H00O), C00Q(H00Q), C00R(H00R)
4.d Idealised Me refined as rotating group:
 C00K(H00F,H00G,H00H), C00S(H00K,H00P,H00S), C4A(H4AA,H4AB,H4AC), C6(H6A,H6B,
 H6C), C1(H1A,H1B,H1C), C6A(H6AA,H6AB,H6AC), C3AA(H3AC,H3AD,H3AE), C3AA(H3AF,
 H3AG,H3AH)
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_shelx_res_checksum              38980
_olex2_submission_special_instructions 'No special instructions were received'