Driving <i>tert</i>-butyl axial: the surprising cyclopropyl effect.
Izzotti, Anthony R.; Gleason, James L.; Chemical science 15 (2024) 18592–18600; doi:10.1039/d4sc05470a

data_1572835
_publ_section_title
;
 Driving <i>tert</i>-butyl axial: the surprising cyclopropyl effect.
;
_journal_issue                   44
_journal_name_full               'Chemical science'
_journal_page_first              18592
_journal_page_last               18600
_journal_paper_doi               10.1039/d4sc05470a
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration rm
_chemical_formula_moiety         'C20 H26 N2, H2 O, 2(C7 H7 O3 S)'
_chemical_formula_sum            'C34 H42 N2 O7 S2'
_chemical_formula_weight         654.81
_chemical_name_systematic
'4,7-dibenzyl-4,7-diazaspiro[2.5]octane-4,7-diium di-4-methylbenzenesulfonate hydrate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-07-31
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.17 svn.r577a77a9 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-08-01 deposited with the CCDC.	2024-10-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 118.580(14)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.120(3)
_cell_length_b                   9.381(2)
_cell_length_c                   14.431(3)
_cell_measurement_reflns_used    4842
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      72.411
_cell_measurement_theta_min      3.488
_cell_volume                     1678.6(7)
_computing_cell_refinement       'Bruker APEX3'
_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'Bruker APEX3'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2019/2 (Sheldrick, 2019)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      298(2)
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measurement_device_type  'Bruker D8'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1585
_diffrn_reflns_av_unetI/netI     0.0952
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            29994
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         72.411
_diffrn_reflns_theta_min         3.488
_exptl_absorpt_coefficient_mu    1.847
_exptl_absorpt_correction_T_max  0.7536
_exptl_absorpt_correction_T_min  0.5385
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'Bruker AXScale'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.296
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.65
_exptl_crystal_size_mid          0.074
_exptl_crystal_size_min          0.053
_refine_diff_density_max         0.255
_refine_diff_density_min         -0.306
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Flack x determined using 1706 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.038(12)
_refine_ls_extinction_coef       0.023(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     445
_refine_ls_number_reflns         6534
_refine_ls_number_restraints     394
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0758
_refine_ls_R_factor_gt           0.0502
_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^)+(0.0666P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1277
_refine_ls_wR_factor_ref         0.1453
_reflns_Friedel_coverage         0.866
_reflns_Friedel_fraction_full    0.988
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                4842
_reflns_number_total             6534
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05470a3.cif
_cod_data_source_block           AI11106
_cod_depositor_comments
'Adding full bibliography for 1572833--1572835.cif.'
_cod_original_cell_volume        1678.5(7)
_cod_database_code               1572835
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.908
_shelx_estimated_absorpt_t_min   0.380
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
S1A \\sim O0AA \\sim O2AA \\sim O1AA: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.02 within 2A
S1A \\sim O4A \\sim O3A \\sim O2A: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C11A) \\sim Ueq, Uanis(O1W) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(O1W) = Uanis(O2W)
2. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
3. Others
 Sof(O0AA)=Sof(O1AA)=Sof(O2AA)=1-FVAR(1)
 Sof(O2A)=Sof(O3A)=Sof(O4A)=FVAR(1)
 Sof(O2W)=Sof(H2WA)=Sof(H2WB)=1-FVAR(2)
 Sof(O1W)=Sof(H1WA)=Sof(H1WB)=FVAR(2)
4.a Free rotating group:
 O1W(H1WA,H1WB), O2W(H2WA,H2WB)
4.b Ternary CH refined with riding coordinates:
 N1(H1), N4(H4)
4.c Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C6(H6A,H6B), C5(H5A,H5B), C9(H9A,H9B), C8(H8A,H8B), C7(H7A,H7B),
 C16(H16A,H16B)
4.d Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), C6A(H6AA), C7A(H7AA), C6B(H6BA), C7B(H7BA),
 C9A(H9AA), C10A(H10A), C9B(H9BA), C10B(H10B)
4.e Idealised Me refined with riding coordinates:
 C11A(H11A,H11B,H11C), C11B(H11D,H11E,H11F)
;
_shelx_res_checksum              67365
_shelx_hkl_checksum              100
_olex2_submission_special_instructions 'No special instructions were received'