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_7125909
_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
'2(C15 H22 O), C15 H18 O, 2(C45 H50 O10), C45 H30.87 O10, C6 H6'
_chemical_formula_sum            'C186 H228 O33'
_chemical_formula_weight         2991.67
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-20
_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                 113.845(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   40.636(4)
_cell_length_b                   12.2639(10)
_cell_length_c                   36.165(3)
_cell_measurement_reflns_used    9972
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      24.99
_cell_measurement_theta_min      2.34
_cell_volume                     16485(3)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      149.98
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker D8 Venture photon II'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0740
_diffrn_reflns_av_unetI/netI     0.0567
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       48
_diffrn_reflns_limit_h_min       -48
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            77612
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.024
_diffrn_reflns_theta_max         25.024
_diffrn_reflns_theta_min         2.337
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.081
_exptl_absorpt_correction_T_max  0.7452
_exptl_absorpt_correction_T_min  0.6889
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1504 before and 0.0662 after correction.
The Ratio of minimum to maximum transmission is 0.9244.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.205
_exptl_crystal_density_meas      ?
_exptl_crystal_description       needle
_exptl_crystal_F_000             6432
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.11
_exptl_transmission_factor_max   0.7452
_exptl_transmission_factor_min   0.6889
_refine_diff_density_max         0.647
_refine_diff_density_min         -0.464
_refine_diff_density_rms         0.076
_refine_ls_extinction_coef       0.0012(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.130
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1167
_refine_ls_number_reflns         14504
_refine_ls_number_restraints     103
_refine_ls_restrained_S_all      1.139
_refine_ls_R_factor_all          0.1722
_refine_ls_R_factor_gt           0.1147
_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^)+(0.2000P)^2^+20.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3159
_refine_ls_wR_factor_ref         0.3730
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8358
_reflns_number_total             14504
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc08728a2.cif
_cod_data_source_block           8
_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_database_code               7125909
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.967
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All O(H,H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C14-C15 = C1-C7 = C7-C8
 1.54 with sigma of 0.01
 C22-O2 = C7-O1A = C7-O1B
 1.42 with sigma of 0.02
 C109-C110 = C111-C112
 1.39 with sigma of 0.01
 C13-C15
 2.52 with sigma of 0.01
3. Rigid bond restraints
 C7, C7, C14, C15, C18, C19, O1A, O1B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
Uanis(C22) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C7) \\sim
Ueq, Uanis(C1) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C15) \\sim Ueq,
Uanis(C17) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C21)
\\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(O1A) \\sim Ueq, Uanis(O2) \\sim Ueq,
Uanis(C11) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C18) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O1A) = Uanis(O1B)
5. Others
 Sof(C80)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=Sof(C93)=Sof(C98)=1-FVAR(1)
 Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=
 Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(H92C)=Sof(C97)=Sof(H97A)=Sof(H97B)=Sof(H97C)=
 FVAR(1)
 Fixed Sof: C17(0.75) H17(0.75) C18(0.75) H18(0.75) C19(0.5) H19(0.5)
 C20(0.75) H20(0.75) C21(0.75) H21(0.75) C70(0.5) C71(0.5) C72(0.75) C73(0.5)
 C74(0.5) C75(0.75) C76(0.5) C77(0.75) C78(0.5) C83(0.5) C84(0.75) C85(0.5)
 C86(0.5) C87(0.75) C88(0.5) C89(0.5) C90(0.75) C91(0.5) C94(0.5) C95(0.75)
 C96(0.5) C99(0.5) C100(0.75) C101(0.5) C102(0.5) C104(0.5) C105(0.75)
 C106(0.5) C107(0.5) C108(0.75) O1A(0.5) O1B(0.5) O2(0.5) H2A(0.5)
6.a Ternary CH refined with riding coordinates:
 C22(H22)
6.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C10(H10D,H10E), C11(H11A,H11B), C12(H12A,H12B),
 C13(H13A,H13B), C14(H14A,H14B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B),
  C34(H34A,H34B), C43(H43A,H43B), C52(H52A,H52B), C61(H61A,H61B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C17(H17), C18(H18), C19(H19),
 C20(H20), C21(H21), C28(H28), C31(H31), C37(H37), C40(H40), C46(H46), C49(H49),
  C55(H55), C58(H58), C64(H64), C67(H67), C109(H109), C110(H110), C111(H111),
 C112(H112)
6.d Fitted hexagon refined as free rotating group:
 C1(C2,C3,C4,C5,C6), C16(C17,C18,C19,C20,C21)
6.e Tetrahedral OH refined with riding coordinates:
 O2(H2A)
6.f Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), 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),
 C79(H79A,H79B,H79C), C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C92(H92A,H92B,
 H92C), C97(H97A,H97B,H97C), C103(H10A,H10B,H10C)
;
_shelx_res_checksum              72281
_olex2_submission_special_instructions 'No special instructions were received'