Unlocking regioselectivity: steric effects and conformational constraints of Lewis bases in alkyllithium-initiated butadiene polymerization.
Tang, Jian; Fu, Yuan; Hua, Jing; Zhang, Jiahao; Peng, Shuoli; Li, Zhibo; Chemical science 15 (2024) 20493–20502; doi:10.1039/d4sc05144k

data_1573238
_publ_section_title
;
 Unlocking regioselectivity: steric effects and conformational constraints
 of Lewis bases in alkyllithium-initiated butadiene polymerization.
;
_journal_issue                   48
_journal_name_full               'Chemical science'
_journal_page_first              20493
_journal_page_last               20502
_journal_paper_doi               10.1039/d4sc05144k
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C15 H29 Li N2'
_chemical_formula_sum            'C15 H29 Li N2'
_chemical_formula_weight         244.34
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Deliquescent,Heat-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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-05-07
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-06-25 deposited with the CCDC.	2024-11-18 downloaded from the CCDC.
;
_cell_angle_alpha                89.051(3)
_cell_angle_beta                 74.903(3)
_cell_angle_gamma                86.783(3)
_cell_formula_units_Z            4
_cell_length_a                   8.9379(3)
_cell_length_b                   12.3047(4)
_cell_length_c                   14.7566(5)
_cell_measurement_reflns_used    8054
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      31.0170
_cell_measurement_theta_min      2.2750
_cell_volume                     1564.42(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.962
_diffrn_measured_fraction_theta_max 0.714
_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    -36.00   8.00   0.50    2.33    --   -6.80  92.00 -69.00   88
  2  \w     -9.00  59.00   0.50    2.33    --   -6.80  37.00 -30.00  136
  3  \w    -79.00   3.00   0.50    2.33    --   -6.80 -57.00-180.00  164
  4  \w    -36.00  11.00   0.50    2.33    --   -6.80 -92.00 177.00   94
  5  \w      3.00  29.00   0.50    2.33    --    3.52 -99.00  60.00   52
  6  \w    -18.00   7.00   0.50    2.33    --    3.52 -99.00 -60.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0721818000
_diffrn_orient_matrix_UB_12      0.0182209000
_diffrn_orient_matrix_UB_13      -0.0267730000
_diffrn_orient_matrix_UB_21      -0.0026262000
_diffrn_orient_matrix_UB_22      -0.0350486000
_diffrn_orient_matrix_UB_23      -0.0371721000
_diffrn_orient_matrix_UB_31      -0.0394773000
_diffrn_orient_matrix_UB_32      0.0421072000
_diffrn_orient_matrix_UB_33      -0.0194931000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0273
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 0.962
_diffrn_reflns_Laue_measured_fraction_max 0.714
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            15299
_diffrn_reflns_point_group_measured_fraction_full 0.962
_diffrn_reflns_point_group_measured_fraction_max 0.714
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.025
_diffrn_reflns_theta_min         2.187
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.059
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50730
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.84a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.037
_exptl_crystal_description       block
_exptl_crystal_F_000             544
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: n-Hexane and toluene'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.682
_refine_diff_density_min         -0.700
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     325
_refine_ls_number_reflns         7137
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0896
_refine_ls_R_factor_gt           0.0728
_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^)+(0.1017P)^2^+1.1499P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1920
_refine_ls_wR_factor_ref         0.2026
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5574
_reflns_number_total             7137
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05144k3.cif
_cod_data_source_block           li6-8mo_auto
_cod_depositor_comments          'Adding full bibliography for 1573238.cif.'
_cod_database_code               1573238
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.991
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Li1-C27
 2.85 with sigma of 0.001
 C10-Li2
 2.85 with sigma of 0.001
3.a Ternary CH refined with riding coordinates:
 C18(H18), C7(H7)
3.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C4(H4A,H4B), C6(H6A,H6B), C8(H8A,H8B), C10(H10A,H10B), C12(H12A,
 H12B), C14(H14A,H14B), C16(H16A,H16B), C20(H20A,H20B), C22(H22A,H22B),
 C24(H24A,H24B), C26(H26A,H26B), C28(H28A,H28B), C30(H30A,H30B), C15(H15A,H15B),
  C2(H2A,H2B), C17(H17A,H17B), C9(H9A,H9B), C19(H19A,H19B), C5(H5A,H5B),
 C21(H21A,H21B), C11(H11A,H11B), C23(H23A,H23B), C3(H3A,H3B), C25(H25A,H25B),
 C13(H13A,H13B), C27(H27A,H27B), C29(H29A,H29B)
;
_shelx_res_checksum              77336
_shelx_hkl_checksum              74663
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.518
_oxdiff_exptl_absorpt_empirical_full_min 0.704