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_1571550
_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 S3'
_chemical_formula_sum            'C26 H44 N2 O4 S3'
_chemical_formula_weight         544.81
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-09-01
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-04-07 deposited with the CCDC.	2024-04-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.5744(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.49888(12)
_cell_length_b                   12.16712(12)
_cell_length_c                   19.36765(17)
_cell_measurement_reflns_used    38924
_cell_measurement_temperature    99.99(13)
_cell_measurement_theta_max      78.1310
_cell_measurement_theta_min      4.1150
_cell_volume                     2944.23(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.65a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.65a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.65a (Rigaku OD, 2022)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(13)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.974
_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    -39.00  26.00   0.50    0.05    --  -47.67  37.00  30.00  130
  2  \w     -7.00  26.00   0.50    0.05    --  -47.67  19.00  30.00   66
  3  \w    -39.00  26.00   0.50    0.05    --  -47.67  36.00-103.00  130
  4  \w     35.00 121.00   0.50    0.05    --   47.67  36.00-103.00  172
  5  \w     37.00 111.00   0.50    0.05    --   47.67  37.00 -30.00  148
  6  \w     75.00 100.00   0.50    0.05    --   47.67  77.00  30.00   50
  7  \w     40.00  73.00   0.50    0.05    --   47.67  77.00  30.00   66
  8  \w     33.00  59.00   0.50    0.05    --   47.67  57.00  30.00   52
  9  \w     98.00 155.00   0.50    0.05    --  110.25  36.00-103.00  114
 10  \w    111.00 178.00   0.50    0.05    --  110.25  30.00-120.00  134
 11  \w     41.00  92.00   0.50    0.05    --  110.25 -77.00 -60.00  102
 12  \w     39.00  67.00   0.50    0.05    --  110.25 -61.00 -90.00   56
 13  \w     45.00  97.00   0.50    0.05    --  110.25 -77.00   0.00  104
 14  \w     38.00  67.00   0.50    0.05    --  110.25 -61.00-180.00   58
 15  \w     41.00  72.00   0.50    0.05    --  110.25 -61.00   0.00   62
 16  \w    -25.00  43.00   0.50    0.05    --   47.67 -36.00 100.00  136
 17  \w     39.00  72.00   0.50    0.05    --  110.25 -61.00 120.00   66
 18  \w     39.00 107.00   0.50    0.05    --  110.25 -77.00 120.00  136
 19  \w     60.00 101.00   0.50    0.05    --  110.25 -94.00  90.00   82
 20  \w     45.00  85.00   0.50    0.05    --  110.25 -94.00   0.00   80
 21  \w     61.00 106.00   0.50    0.05    --  110.25 -94.00 150.00   90
 22  \w    -67.00 -34.00   0.50    0.05    -- -104.00  61.00-150.00   66
 23  \w   -103.00 -62.00   0.50    0.05    -- -104.00  77.00 -90.00   82
 24  \w    -58.00 -31.00   0.50    0.05    -- -104.00  77.00 -90.00   54
 25  \w    -69.00 -38.00   0.50    0.05    -- -104.00  61.00 -90.00   62
 26  \w    -68.00 -34.00   0.50    0.05    -- -104.00  61.00   0.00   68
 27  \w    -64.00 -38.00   0.50    0.05    -- -104.00  61.00  60.00   52
 28  \w    -59.00 -31.00   0.50    0.05    -- -104.00  61.00  90.00   56
 29  \w   -106.00 -80.00   0.50    0.05    -- -104.00 -83.00  62.81   52
 30  \w   -107.00 -80.00   0.50    0.05    -- -104.00 -81.00 -18.13   54
 31  \w   -174.00-148.00   0.50    0.05    -- -104.00 -81.00 -18.13   52
 32  \w   -106.00 -80.00   0.50    0.05    -- -104.00 -81.00  -2.49   52
 33  \w   -106.00 -80.00   0.50    0.05    -- -104.00 -80.00  16.97   52
 34  \w   -105.00 -80.00   0.50    0.05    -- -104.00 -79.00  12.88   50
 35  \w   -106.00 -80.00   0.50    0.05    -- -104.00 -79.00  21.29   52
 36  \w   -109.00 -82.00   0.50    0.05    -- -104.00 -77.00   0.00   54
 37  \w   -107.00 -81.00   0.50    0.05    -- -104.00 -77.00  30.00   52
 38  \w   -106.00 -81.00   0.50    0.05    -- -104.00 -76.00 -32.13   50
 39  \w   -173.00-111.00   0.50    0.05    -- -104.00 -76.00 -32.13  124
 40  \w   -173.00-128.00   0.50    0.05    -- -104.00 -77.00  77.30   90
 41  \w   -121.00 -81.00   0.50    0.05    -- -104.00 -77.00  77.30   80
 42  \w   -108.00 -82.00   0.50    0.05    -- -104.00 -75.00  56.03   52
 43  \w   -108.00 -82.00   0.50    0.05    -- -104.00 -74.00  33.40   52
 44  \w   -112.00 -84.00   0.50    0.05    -- -104.00 -72.00 -18.09   56
 45  \w   -110.00 -83.00   0.50    0.05    -- -104.00 -75.00   0.85   54
 46  \w   -111.00 -84.00   0.50    0.05    -- -104.00 -71.00 -12.77   54
 47  \w   -109.00 -83.00   0.50    0.05    -- -104.00 -72.00  15.97   52
 48  \w   -103.00 -26.00   0.50    0.05    --  -47.67 -77.00  30.00  154
 49  \w   -110.00 -84.00   0.50    0.05    -- -104.00 -70.00  30.60   52
 50  \w   -171.00 -84.00   0.50    0.05    -- -104.00 -69.00  22.04  174
 51  \w   -168.00-142.00   0.50    0.05    -- -104.00 -75.00  56.03   52
 52  \w   -159.00-134.00   0.50    0.05    -- -104.00 -67.00  57.03   50
 53  \w   -130.00 -85.00   0.50    0.05    -- -104.00 -67.00  57.03   90
 54  \w   -116.00 -84.00   0.50    0.05    -- -104.00 -69.00  63.95   64
 55  \w   -116.00 -89.00   0.50    0.05    -- -104.00 -69.00  42.90   54
 56  \w   -115.00 -86.00   0.50    0.05    -- -104.00 -64.00  28.23   58
 57  \w   -112.00 -86.00   0.50    0.05    -- -104.00 -65.00 -32.87   52
 58  \w   -113.00 -86.00   0.50    0.05    -- -104.00 -64.00 -11.55   54
 59  \w   -174.00 -86.00   0.50    0.05    -- -104.00 -66.00  11.92  176
 60  \w   -173.00-148.00   0.50    0.05    -- -104.00 -72.00 -18.09   50
 61  \w   -119.00 -89.00   0.50    0.05    -- -104.00 -58.00  41.40   60
 62  \w   -120.00 -89.00   0.50    0.05    -- -104.00 -57.00  37.13   62
 63  \w   -157.00 -90.00   0.50    0.05    -- -104.00 -48.00  28.06  134
 64  \w   -170.00 -87.00   0.50    0.05    -- -104.00 -61.00 -60.00  166
 65  \w   -122.00 -91.00   0.50    0.05    -- -104.00 -45.00 -60.00   62
 66  \w   -118.00 -91.00   0.50    0.05    -- -104.00 -53.00 -43.80   54
 67  \w   -174.00 -90.00   0.50    0.05    -- -104.00 -59.00 -12.60  168
 68  \w   -121.00 -35.00   0.50    0.05    --  -47.67 -36.00 100.00  172
 69  \w   -175.00 -91.00   0.50    0.05    -- -104.00 -36.00 100.00  168
;
_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      0.0892200000
_diffrn_orient_matrix_UB_12      -0.0585043000
_diffrn_orient_matrix_UB_13      -0.0392777000
_diffrn_orient_matrix_UB_21      0.0719827000
_diffrn_orient_matrix_UB_22      0.0015721000
_diffrn_orient_matrix_UB_23      0.0658531000
_diffrn_orient_matrix_UB_31      -0.0453135000
_diffrn_orient_matrix_UB_32      -0.1122930000
_diffrn_orient_matrix_UB_33      0.0213277000
_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  0.0354
_diffrn_reflns_av_unetI/netI     0.0167
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            58106
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.345
_diffrn_reflns_theta_min         4.158
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.559
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70134
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.65a (Rigaku Oxford Diffraction, 2022)
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    1.229
_exptl_crystal_description       plate
_exptl_crystal_F_000             1176
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.234
_exptl_crystal_size_mid          0.146
_exptl_crystal_size_min          0.031
_refine_diff_density_max         0.444
_refine_diff_density_min         -0.349
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.078
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     326
_refine_ls_number_reflns         6160
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0316
_refine_ls_R_factor_gt           0.0299
_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^)+(0.0424P)^2^+1.2988P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0806
_refine_ls_wR_factor_ref         0.0818
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5736
_reflns_number_total             6160
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4py00160e2.cif
_cod_data_source_block           cx2826
_cod_depositor_comments
'Adding full bibliography for 1571547--1571550.cif.'
_cod_database_code               1571550
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         C26H44N2O4S2
_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:
 C3(H3), C16(H16)
2.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C4(H4A,H4B), C15(H15A,H15B), C17(H17A,H17B)
2.c X=CH2 refined with riding coordinates:
 C12(H12A,H12B), C25(H25A,H25B)
2.d Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C13(H13A,
 H13B,H13C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C),
 C22(H22A,H22B,H22C), C26(H26A,H26B,H26C)
;
_shelx_res_checksum              3943
_shelx_hkl_checksum              13172
_olex2_date_sample_data_collection 2022-08-31
_olex2_date_sample_submission    2022-08-31
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in paratone oil'
_olex2_submission_original_sample_id cx2826
_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 1.417
_oxdiff_exptl_absorpt_empirical_full_min 0.731