BiTEMPS methacrylate dynamic covalent cross-linker providing rapid reprocessability and extrudability of covalent adaptable networks: high-yield synthesis with strong selectivity for disulfide linkages
Debsharma, Tapas; Purwanto, Nathan S.; Fenimore, Logan M.; Mitchell, Sarah; Kennedy, Jayme; Torkelson, John M.; Polymer Chemistry 15 (2024) 2167–2176; doi:10.1039/D4PY00160E

data_1571547
_publ_section_title
;
 BiTEMPS methacrylate dynamic covalent cross-linker providing rapid
 reprocessability and extrudability of covalent adaptable networks:
 high-yield synthesis with strong selectivity for disulfide linkages
;
_journal_issue                   21
_journal_name_full               'Polymer Chemistry'
_journal_page_first              2167
_journal_page_last               2176
_journal_paper_doi               10.1039/D4PY00160E
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C26 H44 N2 O4 S2'
_chemical_formula_sum            'C26 H44 N2 O4 S2'
_chemical_formula_weight         512.75
_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             2023-10-20
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-02-08 deposited with the CCDC.	2024-04-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.9430(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.9420(2)
_cell_length_b                   31.1363(6)
_cell_length_c                   14.2239(2)
_cell_measurement_reflns_used    31686
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      74.4200
_cell_measurement_theta_min      2.8190
_cell_volume                     5730.97(16)
_computing_cell_refinement       'CrysAlisPro 1.171.43.92a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.92a 64-bit (release 05-10-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.92a (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  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.958
_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   -112.00 -28.00   0.50    2.25    --  -49.09 155.00 129.00  168
  2  \w    -88.00  -9.00   0.50    2.25    --  -49.09 119.00 -27.00  158
  3  \w   -120.00 -53.00   0.50    2.25    --  -49.09-155.00  91.00  134
  4  \w    -88.00  -9.00   0.50    2.25    --  -49.09 119.00 -27.00  158
  5  \w     15.00  89.00   0.50    2.25    --   49.09-119.00-112.00  148
  6  \w     59.00 121.00   0.50    2.25    --   49.09 155.00 129.00  124
  7  \w     34.00 114.00   0.50    2.25    --   49.09-155.00  91.00  160
  8  \w     34.00 132.00   0.50    8.99    --  101.75-155.00  91.00  196
  9  \w     59.00 162.00   0.50    8.99    --  101.75 155.00 129.00  206
 10  \w     44.00 104.00   0.50    8.99    --  101.75-119.00-112.00  120
 11  \w    102.00 127.00   0.50    8.99    --  101.75 119.00 -27.00   50
 12  \w   -146.00 -78.00   0.50    8.99    -- -103.00-119.00-112.00  136
 13  \w   -109.00 -65.00   0.50    8.99    -- -103.00 119.00 -27.00   88
 14  \w   -132.00 -32.00   0.50    8.99    -- -103.00 155.00 129.00  200
 15  \w    -30.00  23.00   0.50    2.25    --  -49.09  19.00-180.00  106
 16  \w    -30.00  21.00   0.50    2.25    --  -49.09  19.00 -90.00  102
 17  \w    -27.00  23.00   0.50    2.25    --  -49.09  19.00 -30.00  100
 18  \w   -116.00 -84.00   0.50    2.25    --  -49.09-125.00 -60.00   64
 19  \w    -38.00  23.00   0.50    2.25    --  -49.09  37.00-150.00  122
 20  \w    -29.00  24.00   0.50    2.25    --  -49.09  19.00  60.00  106
 21  \w    -21.00  37.00   0.50    2.25    --   49.09 -19.00-150.00  116
 22  \w     33.00  58.00   0.50    2.25    --   49.09-125.00 120.00   50
 23  \w     31.00  57.00   0.50    8.99    --  101.75 -45.00  90.00   52
 24  \w     31.00  56.00   0.50    8.99    --  101.75 -45.00  30.00   50
 25  \w     30.00  57.00   0.50    8.99    --  101.75 -45.00  60.00   54
 26  \w     95.00 133.00   0.50    8.99    --  101.75  15.00 -90.00   76
 27  \w    149.00 174.00   0.50    8.99    --  101.75  15.00 -90.00   50
 28  \w     30.00  74.00   0.50    8.99    --  101.75 -94.00 -60.00   88
 29  \w     94.00 121.00   0.50    8.99    --  101.75  15.00  90.00   54
 30  \w     30.00  56.00   0.50    8.99    --  101.75 -45.00 -60.00   52
 31  \w     31.00  73.00   0.50    8.99    --  101.75 -61.00  30.00   84
 32  \w     74.00 106.00   0.50    8.99    --  101.75 -94.00  30.00   64
 33  \w    137.00 174.00   0.50    8.99    --  101.75  15.00  90.00   74
 34  \w     34.00  72.00   0.50    8.99    --  101.75-125.00  30.00   76
 35  \w     72.00 101.00   0.50    8.99    --  101.75 -94.00 -90.00   58
 36  \w     36.00  68.00   0.50    8.99    --  101.75 -94.00 -90.00   64
 37  \w    102.00 130.00   0.50    8.99    --  101.75-155.00  91.00   56
 38  \w     94.00 171.00   0.50    8.99    --  101.75 125.00   0.00  154
 39  \w     33.00  95.00   0.50    8.99    --  101.75-125.00  90.00  124
 40  \w     34.00  73.00   0.50    8.99    --  101.75 -61.00 120.00   78
;
_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      -0.1103294000
_diffrn_orient_matrix_UB_12      0.0167945000
_diffrn_orient_matrix_UB_13      -0.0190112000
_diffrn_orient_matrix_UB_21      -0.0370245000
_diffrn_orient_matrix_UB_22      -0.0462150000
_diffrn_orient_matrix_UB_23      -0.0198472000
_diffrn_orient_matrix_UB_31      -0.0250121000
_diffrn_orient_matrix_UB_32      -0.0056525000
_diffrn_orient_matrix_UB_33      0.1047548000
_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  0.0802
_diffrn_reflns_av_unetI/netI     0.0373
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            82193
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.046
_diffrn_reflns_theta_min         2.838
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.936
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.726
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.92a (Rigaku Oxford Diffraction, 2023)
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    1.189
_exptl_crystal_description       needle
_exptl_crystal_F_000             2224
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.192
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.008
_refine_diff_density_max         0.653
_refine_diff_density_min         -0.549
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     633
_refine_ls_number_reflns         11460
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0854
_refine_ls_R_factor_gt           0.0681
_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^)+(0.0324P)^2^+14.7953P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1527
_refine_ls_wR_factor_ref         0.1599
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8956
_reflns_number_total             11460
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4py00160e2.cif
_cod_data_source_block           cx3242
_cod_depositor_comments
'Adding full bibliography for 1571547--1571550.cif.'
_cod_database_code               1571547
_shelx_shelxl_version_number     2019/1
_chemical_oxdiff_formula         C26H44N2O4S2
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.708
_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.a Ternary CH refined with riding coordinates:
 C5(H5), C16(H16), C5A(H5A), C16A(H16A)
2.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C9(H9A,H9B), C15(H15A,H15B), C17(H17A,H17B), C6A(H6AA,H6AB),
 C9A(H9AA,H9AB), C15A(H15C,H15D), C17A(H17C,H17D)
2.c X=CH2 refined with riding coordinates:
 C3(H3A,H3B), C26(H26A,H26B), C1A(H1AA,H1AB), C26A(H26C,H26D)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,
 H12C), C13(H13A,H13B,H13C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,
 H21B,H21C), C22(H22A,H22B,H22C), C25(H25A,H25B,H25C), C3A(H3AA,H3AB,H3AC),
 C10A(H10D,H10E,H10F), C11A(H11D,H11E,H11F), C12A(H12D,H12E,H12F), C13A(H13D,
 H13E,H13F), C19A(H19D,H19E,H19F), C20A(H20D,H20E,H20F), C21A(H21D,H21E,H21F),
 C22A(H22D,H22E,H22F), C25A(H25D,H25E,H25F)
;
_shelx_res_checksum              41464
_shelx_hkl_checksum              62060
_olex2_date_sample_data_collection 2023-10-19
_olex2_date_sample_submission    2023-10-18
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in paratone oil'
_olex2_submission_original_sample_id cx3242
_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 1.763
_oxdiff_exptl_absorpt_empirical_full_min 0.651