Combining alkali metals and zinc to harness heterometallic cooperativity in cyclic ester ring-opening polymerisation
Gruszka, Weronika; Lykkeberg, Anna; Nichol, Gary S.; Shaver, Michael P.; Buchard, Antoine; Garden, Jennifer A.; Chemical Science  (2020) –; doi:10.1039/D0SC04705H

data_1559335
_publ_section_title
;
 Combining alkali metals and zinc to harness heterometallic cooperativity
 in cyclic ester ring-opening polymerisation
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC04705H
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C51 H61 N2 Na O5, 2(C4 H8 O)'
_chemical_formula_sum            'C59 H77 N2 Na O7'
_chemical_formula_weight         949.21
_space_group_crystal_system      tetragonal
_space_group_IT_number           78
_space_group_name_Hall           'P 4cw'
_space_group_name_H-M_alt        'P 43'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-05-04
_audit_creation_method
;
Olex2 1.3-beta
(compiled 2020.04.02 svn.r1fbe7b6f for OlexSys, GUI svn.r6076)
;
_audit_update_record
;
2020-05-07 deposited with the CCDC.	2020-10-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.8142(4)
_cell_length_b                   9.8142(4)
_cell_length_c                   54.0271(12)
_cell_measurement_reflns_used    15205
_cell_measurement_temperature    120.0
_cell_measurement_theta_max      74.8770
_cell_measurement_theta_min      4.4630
_cell_volume                     5203.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.61a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.0
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.8095
_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    -75.00  34.00   1.00   25.00    --  -41.67  83.00-128.00  109
  2  \w    -12.00  75.00   1.00   25.00    --   41.67 -83.00 111.00   87
  3  \w     34.00 144.00   1.00   30.00    --  111.00 -83.00 111.00  110
  4  \w    100.00 178.00   1.00   30.00    --  111.00  83.00-128.00   78
  5  \w    -68.00  28.00   1.00   25.00    --  -41.67  57.00 120.00   96
  6  \w   -112.00 -15.00   1.00   25.00    --  -41.67 -57.00 -30.00   97
  7  \w   -126.00 -37.00   1.00   25.00    --  -41.67 178.00  90.00   89
  8  \w     10.00  42.00   1.00   25.00    --   41.67  78.00 -72.37   32
  9  \w    103.00 178.00   1.00   30.00    --  111.00  77.00 -90.00   75
 10  \w     40.00 135.00   1.00   30.00    --  111.00 -45.00  90.00   95
 11  \w     97.00 178.00   1.00   30.00    --  111.00 125.00  60.00   81
 12  \w     87.00 178.00   1.00   30.00    --  111.00  30.00  60.00   91
 13  \w    103.00 178.00   1.00   30.00    --  111.00  77.00   0.00   75
 14  \w     39.00 112.00   1.00   30.00    --  111.00-125.00 -30.00   73
 15  \w     39.00 112.00   1.00   30.00    --  111.00-125.00 120.00   73
 16  \w     97.00 178.00   1.00   30.00    --  111.00 125.00  90.00   81
 17  \w     39.00 112.00   1.00   30.00    --  111.00-125.00-120.00   73
 18  \w     39.00 112.00   1.00   30.00    --  111.00-125.00-180.00   73
 19  \w     39.00 112.00   1.00   30.00    --  111.00-125.00  90.00   73
 20  \w     39.00 112.00   1.00   30.00    --  111.00-125.00 -60.00   73
 21  \w     39.00 112.00   1.00   30.00    --  111.00-125.00   0.00   73
 22  \w     87.00 178.00   1.00   30.00    --  111.00  45.00-180.00   91
 23  \w     97.00 178.00   1.00   30.00    --  111.00 125.00-180.00   81
 24  \w     97.00 178.00   1.00   30.00    --  111.00 125.00 120.00   81
 25  \w   -112.00 -15.00   1.00   25.00    --  -41.67 -57.00-120.00   97
 26  \w   -112.00 -15.00   1.00   25.00    --  -41.67 -57.00 150.00   97
 27  \w   -112.00 -15.00   1.00   25.00    --  -41.67 -57.00  60.00   97
 28  \w   -128.00 -39.00   1.00   25.00    --  -41.67-178.00-120.00   89
 29  \w     10.00  42.00   1.00   25.00    --   41.67  80.00 106.94   32
 30  \w     83.00 167.00   1.00   30.00    --  111.00  61.00 120.00   84
 31  \w     83.00 178.00   1.00   30.00    --  111.00  61.00 -30.00   95
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku Oxford Diffraction SuperNova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1287592000
_diffrn_orient_matrix_UB_12      0.0595515000
_diffrn_orient_matrix_UB_13      0.0121855000
_diffrn_orient_matrix_UB_21      0.0080028000
_diffrn_orient_matrix_UB_22      0.1245964000
_diffrn_orient_matrix_UB_23      -0.0173030000
_diffrn_orient_matrix_UB_31      -0.0894283000
_diffrn_orient_matrix_UB_32      -0.0745097000
_diffrn_orient_matrix_UB_33      -0.0191104000
_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  0.0622
_diffrn_reflns_av_unetI/netI     0.0721
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       64
_diffrn_reflns_limit_l_min       -64
_diffrn_reflns_number            10795
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.239
_diffrn_reflns_theta_min         4.505
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.689
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.36699
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.61a (Rigaku Oxford Diffraction, 2019)
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    1.212
_exptl_crystal_description       plate
_exptl_crystal_F_000             2048
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of THF and toluene  by slow cooling'
_exptl_crystal_size_max          0.122
_exptl_crystal_size_mid          0.062
_exptl_crystal_size_min          0.039
_refine_diff_density_max         0.259
_refine_diff_density_min         -0.265
_refine_diff_density_rms         0.056
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.06(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.972
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     626
_refine_ls_number_reflns         10795
_refine_ls_number_restraints     71
_refine_ls_restrained_S_all      0.975
_refine_ls_R_factor_all          0.0928
_refine_ls_R_factor_gt           0.0690
_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^)+(0.1117P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1656
_refine_ls_wR_factor_ref         0.1760
_reflns_Friedel_coverage         0.975
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                7788
_reflns_number_total             10795
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.4464\% 
 around [1.00 -0.00 -0.00] (reciprocal) or [1.00 -0.00 -0.00] (direct)
;
_cod_data_source_file            d0sc04705h2.cif
_cod_data_source_block           1
_cod_original_cell_volume        5203.8(4)
_cod_database_code               1559335
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C61 H79 N2 Na1 O5'
_chemical_oxdiff_usercomment     '@ 120 K '
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.500(3)
 0.500(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
O7 \\sim C56 \\sim C57 \\sim C58 \\sim C59: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 O7, C56, C57, C58, C59
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{O6, C52, C53, C54, C55} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O7, C56, C57, C58, C59}
6.a Ternary CH refined with riding coordinates:
 C2(H2), C27(H27)
6.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C18(H18A,H18B), C28(H28A,H28B),
 C29(H29A,H29B), C30(H30A,H30B), C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B),
  C46(H46A,H46B), C47(H47A,H47B), C48(H48A,H48B), C49(H49A,H49B), C50(H50A,
 H50B), C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B),
 C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B)
6.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17), C21(H21), C23(H23), C32(H32), C33(H33), C34(H34), C35(H35),
  C36(H36), C38(H38), C39(H39), C40(H40), C41(H41), C42(H42)
6.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C)
6.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O3(H3)
;
_shelx_res_checksum              24080
_olex2_date_sample_data_collection 2019-12-02
_olex2_date_sample_submission    2019-11-20
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems Cryostream 700+'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil.'
_olex2_submission_original_sample_id WG-03-37
_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 1.705
_oxdiff_exptl_absorpt_empirical_full_min 0.559
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2