Stabilization of Grignard reagents by a pillar[5]arene host - Schlenk equilibria and Grignard reactions.
Shen, Lingyi; Zhao, Yanxia; Dai, Dihua; Yang, Ying-Wei; Wu, Biao; Yang, Xiao-Juan; Chemical communications (Cambridge, England) 56 (2020) 1381–1384; doi:10.1039/c9cc08728a

data_7125910
_publ_section_title
;
 Stabilization of Grignard reagents by a pillar[5]arene host - Schlenk
 equilibria and Grignard reactions.
;
_journal_issue                   9
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              1381
_journal_page_last               1384
_journal_paper_doi               10.1039/c9cc08728a
_journal_volume                  56
_journal_year                    2020
_chemical_formula_moiety         'C22.57 H45.49 Br0.36 Mg2 O2, C45 H50 O10'
_chemical_formula_sum            'C67.57 H98.78 Br0.36 Mg2 O12'
_chemical_formula_weight         1180.46
_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   geom
_audit_creation_date             2019-04-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-07-23 deposited with the CCDC.	2020-01-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.915(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.565(3)
_cell_length_b                   12.450(3)
_cell_length_c                   20.554(4)
_cell_measurement_reflns_used    8068
_cell_measurement_temperature    153(2)
_cell_measurement_theta_max      24.45
_cell_measurement_theta_min      2.19
_cell_volume                     3302.9(13)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      153.15
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0383
_diffrn_reflns_av_unetI/netI     0.0656
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            20588
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.939
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.312
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.4622
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.1229 before and 0.0668 after correction.
The Ratio of minimum to maximum transmission is 0.6202.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.187
_exptl_crystal_density_meas      ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1274
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_exptl_transmission_factor_max   0.7452
_exptl_transmission_factor_min   0.4622
_refine_diff_density_max         0.504
_refine_diff_density_min         -1.078
_refine_diff_density_rms         0.083
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.43(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     755
_refine_ls_number_reflns         11320
_refine_ls_number_restraints     80
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0996
_refine_ls_R_factor_gt           0.0768
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1675P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2181
_refine_ls_wR_factor_ref         0.2354
_reflns_Friedel_coverage         0.908
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                8704
_reflns_number_total             11320
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc08728a2.cif
_cod_data_source_block           2
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_crystal_density_meas' value 'not measured' was
changed to '?' -- the value is perceived as not measured.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 
;
_cod_original_cell_volume        3302.9(11)
_cod_database_code               7125910
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.940
_shelx_estimated_absorpt_t_min   0.912
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.57(4)
 0.43(4)
2. 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
3. Restrained distances
 C13-C14 = C14-C15 = C15-C16
 1.54 with sigma of 0.02
 C5-C6
 1.54 with sigma of 0.01
 C7-C8
 1.54 with sigma of 0.02
 C13-C15
 2.52 with sigma of 0.04
4. Rigid bond restraints
 C13, C14, C15, C16
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C5, C6
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C7, C8
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Uiso/Uaniso restraints and constraints
C13 \\sim C14 \\sim C15 \\sim C16: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002
Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C16)
\\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C12) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C17) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C18) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C15) = Uanis(C16)
Uanis(C14) = Uanis(C15)
Uanis(C13) = Uanis(Br1)
6. Others
 Sof(C13)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(C16)=
 Sof(H16A)=Sof(H16B)=Sof(H16C)=1-FVAR(1)
 Sof(Br1)=FVAR(1)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C6(H6A,H6B), C7(H7A,H7B), C9(H9A,H9B),
 C10(H10A,H10B), C11(H11A,H11B), C14(H14A,H14B), C15(H15A,H15B), C17(H17A,H17B),
  C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,
 H22B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C34(H34A,H34B),
 C43(H43A,H43B), C52(H52A,H52B), C61(H61A,H61B)
7.b Aromatic/amide H refined with riding coordinates:
 C27(H27), C30(H30), C36(H36), C39(H39), C45(H45), C48(H48), C54(H54),
 C57(H57), C63(H63), C66(H66)
7.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C8(H8A,H8B,H8C), C12(H12A,H12B,H12C), C16(H16A,H16B,H16C),
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C41(H41A,H41B,H41C), C42(H42A,H42B,
 H42C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C59(H59A,H59B,H59C), C60(H60A,
 H60B,H60C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C)
;
_shelx_res_checksum              52566
_olex2_submission_special_instructions 'No special instructions were received'