Alkali metal reduction of crown ether encapsulated alkali metal cations.
Pearce, Kyle G.; Neale, Samuel E.; Mahon, Mary F.; McMullin, Claire L.; Hill, Michael S.; Chemical communications (Cambridge, England) 60 (2024) 8391–8394; doi:10.1039/d4cc02725f

data_7133277
_publ_section_title
;
 Alkali metal reduction of crown ether encapsulated alkali metal cations.
;
_journal_issue                   64
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              8391
_journal_page_last               8394
_journal_paper_doi               10.1039/d4cc02725f
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety
'2(C30 H50 Be Cl N2 Si2), C12 H24 Li O6, C16 H32 Li O8, C6 H6'
_chemical_formula_sum            'C94 H162 Be2 Cl2 Li2 N4 O14 Si4'
_chemical_formula_weight         1787.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-05-30
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-05-19 deposited with the CCDC.	2024-07-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.6680(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.4089(2)
_cell_length_b                   22.3190(2)
_cell_length_c                   22.5227(2)
_cell_measurement_reflns_used    60398
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      73.2190
_cell_measurement_theta_min      4.0160
_cell_volume                     10499.94(17)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1150
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0300
_diffrn_reflns_av_unetI/netI     0.0155
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            146394
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.436
_diffrn_reflns_theta_min         3.783
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.444
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.615
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.131
_exptl_crystal_description       block
_exptl_crystal_F_000             3880
_exptl_crystal_size_max          0.286
_exptl_crystal_size_mid          0.195
_exptl_crystal_size_min          0.158
_refine_diff_density_max         0.738
_refine_diff_density_min         -0.414
_refine_diff_density_rms         0.039
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1477
_refine_ls_number_reflns         21025
_refine_ls_number_restraints     1434
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0470
_refine_ls_R_factor_gt           0.0425
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0557P)^2^+5.1570P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1115
_refine_ls_wR_factor_ref         0.1155
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18894
_reflns_number_total             21025
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc02725f2.cif
_cod_data_source_block           s22msh59-cpd-6
_cod_depositor_comments
'Adding full bibliography for 7133277--7133282.cif.'
_cod_database_code               7133277
_shelxl_version_number           2014-3
_olex2_refinement_description
;
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
2. Restrained distances
 O5A-C42A = O5-C42 = O5A-C43A = O5-C43 = O6A-C44A = O6-C44 = O6A-C37A = O6-C37
 = O7A-C38A = O7-C38 = O7A-C39A = O7-C39 = O8A-C40A = O8-C40 = O8A-C41A = O8-C41
 1.4 with sigma of 0.005
 C42A-C41A = C42-C41 = C44-C43 = C44A-C43A = C38-C37 = C38A-C37A = C40-C39 =
 C40A-C39A
 1.54 with sigma of 0.005
 O2-O3 \\sim O4-O1
 with sigma of 0.005
 C36-O3 \\sim O12-C80
 with sigma of 0.005
 C36-Li1 \\sim C36A-Li1
 with sigma of 0.01
 O4-C32 \\sim O4A-C32A
 with sigma of 0.01
 O4-Li1 \\sim O4A-Li1
 with sigma of 0.01
 O4-C33 \\sim O4A-C33A
 with sigma of 0.01
 C34-Li1 \\sim C34A-Li1
 with sigma of 0.01
 O1-C30 \\sim O1A-C30A
 with sigma of 0.01
 O1-C31 \\sim O1A-C31A
 with sigma of 0.01
 O1-Li1 \\sim O1A-Li1
 with sigma of 0.01
 C30-C31 \\sim C30A-C31A
 with sigma of 0.01
 C32-C31 \\sim C32A-C31A
 with sigma of 0.01
 C32-C33 \\sim C32A-C33A
 with sigma of 0.01
 O2-C36 \\sim O2A-C36A
 with sigma of 0.01
 O2-C29 \\sim O2A-C29A
 with sigma of 0.01
 O2-C35 \\sim O2A-C35A
 with sigma of 0.01
 O2-Li1 \\sim O2A-Li1
 with sigma of 0.01
 C36-C35 \\sim C36A-C35A
 with sigma of 0.01
 C31-Li1 \\sim C31A-Li1
 with sigma of 0.01
 C30-C29 \\sim C30A-C29A
 with sigma of 0.01
 C33-Li1 \\sim C33A-Li1
 with sigma of 0.01
 C34-C33 \\sim C34A-C33A
 with sigma of 0.01
 C34-O3 \\sim C34A-O3A
 with sigma of 0.01
 C32-Li1 \\sim C32A-Li1
 with sigma of 0.01
 O2-C30 \\sim O2A-C30A
 with sigma of 0.01
 C35-O3 \\sim C35A-O3A
 with sigma of 0.01
 C36-C29 \\sim C36A-C29A
 with sigma of 0.01
 C36-O3 \\sim C36A-O3A
 with sigma of 0.01
 C30-Li1 \\sim C30A-Li1
 with sigma of 0.01
 C34-C35 \\sim C34A-C35A
 with sigma of 0.01
 Li1-O3 \\sim Li1-O3A
 with sigma of 0.01
 O4-C34 \\sim O4A-C34A
 with sigma of 0.01
 O4-C31 \\sim O4A-C31A
 with sigma of 0.01
 C35-Li1 \\sim C35A-Li1
 with sigma of 0.01
 C33-O3 \\sim C33A-O3A
 with sigma of 0.01
 O1-C32 \\sim O1A-C32A
 with sigma of 0.01
 C29-Li1 \\sim C29A-Li1
 with sigma of 0.01
 O1-C29 \\sim O1A-C29A
 with sigma of 0.01
 O6-C38 \\sim O6A-C38A
 with sigma of 0.01
 O5-C44 \\sim O5A-C44A
 with sigma of 0.01
 C42-C43 \\sim C42A-C43A
 with sigma of 0.01
 O8-C42 \\sim O8A-C42A
 with sigma of 0.01
 O7-C39 \\sim O7A-C39A
 with sigma of 0.01
 O7-Li1 \\sim O7A-Li1
 with sigma of 0.01
 O7-C38 \\sim O7A-C38A
 with sigma of 0.01
 C39-C38 \\sim C39A-C38A
 with sigma of 0.01
 C41-Li1 \\sim C41A-Li1
 with sigma of 0.01
 O8-C41 \\sim O8A-C41A
 with sigma of 0.01
 O8-C40 \\sim O8A-C40A
 with sigma of 0.01
 C37-C44 \\sim C37A-C44A
 with sigma of 0.01
 O5-C42 \\sim O5A-C42A
 with sigma of 0.01
 O5-C43 \\sim O5A-C43A
 with sigma of 0.01
 O5-Li1 \\sim O5A-Li1
 with sigma of 0.01
 O6-C37 \\sim O6A-C37A
 with sigma of 0.01
 O6-C44 \\sim O6A-C44A
 with sigma of 0.01
 O6-Li1 \\sim O6A-Li1
 with sigma of 0.01
 O8-C39 \\sim O8A-C39A
 with sigma of 0.01
 O5-C41 \\sim O5A-C41A
 with sigma of 0.01
 C39-C40 \\sim C39A-C40A
 with sigma of 0.01
 C41-C42 \\sim C41A-C42A
 with sigma of 0.01
 O6-C43 \\sim O6A-C43A
 with sigma of 0.01
 C39-Li1 \\sim C39A-Li1
 with sigma of 0.01
 C40-Li1 \\sim C40A-Li1
 with sigma of 0.01
 C37-C38 \\sim C37A-C38A
 with sigma of 0.01
 C42-Li1 \\sim C42A-Li1
 with sigma of 0.01
 C43-C44 \\sim C43A-C44A
 with sigma of 0.01
 C37-Li1 \\sim C37A-Li1
 with sigma of 0.01
 C43-Li1 \\sim C43A-Li1
 with sigma of 0.01
 C44-Li1 \\sim C44A-Li1
 with sigma of 0.01
 Li1-C38 \\sim Li1-C38A
 with sigma of 0.01
 O7-C40 \\sim O7A-C40A
 with sigma of 0.01
 O7-C37 \\sim O7A-C37A
 with sigma of 0.01
 C75-C82 \\sim C75A-C82A
 with sigma of 0.01
 O12-C79 \\sim O12A-C79A
 with sigma of 0.01
 O12-C78 \\sim O12A-C78A
 with sigma of 0.01
 O12-Li2 \\sim O12A-Li2
 with sigma of 0.01
 C80-Li2 \\sim C80A-Li2
 with sigma of 0.01
 O10-C75 \\sim O10A-C75A
 with sigma of 0.01
 O10-C82 \\sim O10A-C82A
 with sigma of 0.01
 O9-C78 \\sim O9A-C78A
 with sigma of 0.01
 O10-Li2 \\sim O10A-Li2
 with sigma of 0.01
 O9-C77 \\sim O9A-C77A
 with sigma of 0.01
 O9-C76 \\sim O9A-C76A
 with sigma of 0.01
 O9-Li2 \\sim O9A-Li2
 with sigma of 0.01
 O11-C80 \\sim O11A-C80A
 with sigma of 0.01
 C81-C80 \\sim C81A-C80A
 with sigma of 0.01
 C79-Li2 \\sim C79A-Li2
 with sigma of 0.01
 C81-C82 \\sim C81A-C82A
 with sigma of 0.01
 C77-Li2 \\sim C77A-Li2
 with sigma of 0.01
 C79-C80 \\sim C79A-C80A
 with sigma of 0.01
 C75-C76 \\sim C75A-C76A
 with sigma of 0.01
 C77-C78 \\sim C77A-C78A
 with sigma of 0.01
 O9-C75 \\sim O9A-C75A
 with sigma of 0.01
 C81-Li2 \\sim C81A-Li2
 with sigma of 0.01
 O11-C81 \\sim O11A-C81A
 with sigma of 0.01
 C79-C78 \\sim C79A-C78A
 with sigma of 0.01
 C75-Li2 \\sim C75A-Li2
 with sigma of 0.01
 C77-C76 \\sim C77A-C76A
 with sigma of 0.01
 O11-C79 \\sim O11A-C79A
 with sigma of 0.01
 O11-C82 \\sim O11A-C82A
 with sigma of 0.01
 C82-Li2 \\sim C82A-Li2
 with sigma of 0.01
 O12-C77 \\sim O12A-C77A
 with sigma of 0.01
 O12-C80 \\sim O12A-C80A
 with sigma of 0.01
 C78-Li2 \\sim C78A-Li2
 with sigma of 0.01
 C76-Li2 \\sim C76A-Li2
 with sigma of 0.01
 O10-C81 \\sim O10A-C81A
 with sigma of 0.01
 O10-C76 \\sim O10A-C76A
 with sigma of 0.01
 O11-Li2 \\sim O11A-Li2
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C87A \\sim C91A \\sim C90A \\sim C92A \\sim C89A \\sim C88A \\sim C92 \\sim C91
\\sim C90 \\sim C89 \\sim C87 \\sim C88: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.01 within 2A
O4 \\sim O1 \\sim C32 \\sim O2 \\sim C36 \\sim C30 \\sim C34 \\sim C31 \\sim
C35 \\sim C33 \\sim C29 \\sim O3 \\sim O3A \\sim O1A \\sim O2A \\sim C36A \\sim
C30A \\sim C29A \\sim C35A \\sim C31A \\sim C32A \\sim C33A \\sim C34A \\sim
O4A: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.01 within 2A
O7 \\sim O8 \\sim O5 \\sim O6 \\sim C39 \\sim C41 \\sim C40 \\sim C42 \\sim C37
\\sim C43 \\sim C44 \\sim C38 \\sim C37A \\sim C38A \\sim C40A \\sim C44A \\sim
C42A \\sim C41A \\sim C43A \\sim O5A \\sim O6A \\sim O7A \\sim C39A \\sim O8A:
within 2A with sigma of 0.015 and sigma for terminal atoms of 0.01 within 2A
O8A \\sim O8: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.01
within 2A
O11 \\sim O12 \\sim O10 \\sim O9 \\sim C81 \\sim C79 \\sim C75 \\sim C77 \\sim
C80 \\sim C82 \\sim C78 \\sim C76 \\sim C79A \\sim C81A \\sim O11A \\sim O12A
\\sim C82A \\sim C78A \\sim O10A \\sim C77A \\sim C76A \\sim C75A \\sim O9A
\\sim C80A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.01
within 2A
4. Others
 Fixed Sof: O9(0.75) O10(0.75) O11(0.75) O12(0.75) C75(0.75) H75A(0.75)
 H75B(0.75) C76(0.75) H76A(0.75) H76B(0.75) C77(0.75) H77A(0.75) H77B(0.75)
 C78(0.75) H78A(0.75) H78B(0.75) C79(0.75) H79A(0.75) H79B(0.75) C80(0.75)
 H80A(0.75) H80B(0.75) C81(0.75) H81A(0.75) H81B(0.75) C82(0.75) H82A(0.75)
 H82B(0.75) O9A(0.25) O10A(0.25) O11A(0.25) O12A(0.25) C75A(0.25) H75C(0.25)
 H75D(0.25) C76A(0.25) H76C(0.25) H76D(0.25) C77A(0.25) H77C(0.25) H77D(0.25)
 C78A(0.25) H78C(0.25) H78D(0.25) C79A(0.25) H79C(0.25) H79D(0.25) C80A(0.25)
 H80C(0.25) H80D(0.25) C81A(0.25) H81C(0.25) H81D(0.25) C82A(0.25) H82C(0.25)
 H82D(0.25) O1(0.67) O2(0.67) O3(0.67) O4(0.67) O5(0.5) O6(0.5) O7(0.5) O8(0.5)
 C29(0.67) H29A(0.67) H29B(0.67) C30(0.67) H30A(0.67) H30B(0.67) C31(0.67)
 H31A(0.67) H31B(0.67) C32(0.67) H32A(0.67) H32B(0.67) C33(0.67) H33A(0.67)
 H33B(0.67) C34(0.67) H34A(0.67) H34B(0.67) C35(0.67) H35A(0.67) H35B(0.67)
 C36(0.67) H36A(0.67) H36B(0.67) C37(0.5) H37A(0.5) H37B(0.5) C38(0.5)
 H38A(0.5) H38B(0.5) C39(0.5) H39A(0.5) H39B(0.5) C40(0.5) H40A(0.5) H40B(0.5)
 C41(0.5) H41A(0.5) H41B(0.5) C42(0.5) H42A(0.5) H42B(0.5) C43(0.5) H43A(0.5)
 H43B(0.5) C44(0.5) H44A(0.5) H44B(0.5) O1A(0.33) O2A(0.33) O3A(0.33) O4A(0.33)
 O5A(0.5) O6A(0.5) O7A(0.5) O8A(0.5) C29A(0.33) H29C(0.33) H29D(0.33)
 C30A(0.33) H30C(0.33) H30D(0.33) C31A(0.33) H31C(0.33) H31D(0.33) C32A(0.33)
 H32C(0.33) H32D(0.33) C33A(0.33) H33C(0.33) H33D(0.33) C34A(0.33) H34C(0.33)
 H34D(0.33) C35A(0.33) H35C(0.33) H35D(0.33) C36A(0.33) H36C(0.33) H36D(0.33)
 C37A(0.5) H37C(0.5) H37D(0.5) C38A(0.5) H38C(0.5) H38D(0.5) C39A(0.5)
 H39C(0.5) H39D(0.5) C40A(0.5) H40C(0.5) H40D(0.5) C41A(0.5) H41C(0.5)
 H41D(0.5) C42A(0.5) H42C(0.5) H42D(0.5) C43A(0.5) H43C(0.5) H43D(0.5)
 C44A(0.5) H44C(0.5) H44D(0.5) C91(0.5) H91(0.5) C90(0.5) H90(0.5) C89(0.5)
 H89(0.5) C88(0.5) H88(0.5) C87(0.5) H87(0.5) C92(0.5) H92(0.5) C91A(0.5)
 H91A(0.5) C90A(0.5) H90A(0.5) C89A(0.5) H89A(0.5) C88A(0.5) H88A(0.5)
 C87A(0.5) H87A(0.5) C92A(0.5) H92A(0.5)
5.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C23(H23), C26(H26), C55(H55), C58(H58), C69(H69), C72(H72)
5.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C45(H45A,H45B), C46(H46A,H46B), C83(H83A,H83B),
 C84(H84A,H84B), C85(H85A,H85B), C86(H86A,H86B), C75(H75A,H75B), C76(H76A,H76B),
  C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B), C81(H81A,
 H81B), C82(H82A,H82B), C75A(H75C,H75D), C76A(H76C,H76D), C77A(H77C,H77D),
 C78A(H78C,H78D), C79A(H79C,H79D), C80A(H80C,H80D), C81A(H81C,H81D), C82A(H82C,
 H82D), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B),
 C33(H33A,H33B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B),
  C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,
 H42B), C43(H43A,H43B), C44(H44A,H44B), C29A(H29C,H29D), C30A(H30C,H30D),
 C31A(H31C,H31D), C32A(H32C,H32D), C33A(H33C,H33D), C34A(H34C,H34D), C35A(H35C,
 H35D), C36A(H36C,H36D), C37A(H37C,H37D), C38A(H38C,H38D), C39A(H39C,H39D),
 C40A(H40C,H40D), C41A(H41C,H41D), C42A(H42C,H42D), C43A(H43C,H43D), C44A(H44C,
 H44D)
5.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C19(H19), C20(H20), C21(H21), C51(H51), C52(H52),
 C53(H53), C65(H65), C66(H66), C67(H67), C91(H91), C90(H90), C89(H89), C88(H88),
  C87(H87), C92(H92), C91A(H91A), C90A(H90A), C89A(H89A), C88A(H88A),
 C87A(H87A), C92A(H92A)
5.d Fitted hexagon refined as free rotating group:
 C91(C90,C89,C88,C87,C92), C91A(C90A,C89A,C88A,C87A,C92A)
5.e Idealised Me refined as rotating group:
 C01T(H01A,H01B,H01C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C24(H24A,H24B,
 H24C), C25(H25A,H25B,H25C), C026(H02A,H02B,H02C), C27(H27A,H27B,H27C),
 C28(H28A,H28B,H28C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C56(H56A,H56B,
 H56C), C57(H57A,H57B,H57C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C61(H61A,
 H61B,H61C), C62(H62A,H62B,H62C), C70(H70A,H70B,H70C), C71(H71A,H71B,H71C),
 C73(H73A,H73B,H73C), C74(H74A,H74B,H74C)
;
_shelx_res_checksum              86925
_shelx_hkl_checksum              1902