Stress-Responsive Polymers Containing Cyclobutane Core Mechanophores: Reactivity and Mechanistic Insights
Zachary S. Kean; Zhenbin Niu; Gihan B. Hewage; Arnold L. Rheingold; Stephen L. Craig; Journal of the American Chemical Society 135 (2013) 13598–13604; doi:10.1021/ja4075997

data_4120781
_publ_contact_author_name
;
;
_publ_section_title
;
 Stress-Responsive Polymers Containing Cyclobutane Core Mechanophores:
 Reactivity and Mechanistic Insights
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13598
_journal_page_last               13604
_journal_paper_doi               10.1021/ja4075997
_journal_volume                  135
_journal_year                    2013
_chemical_formula_moiety         'C13 H17 N O4'
_chemical_formula_sum            'C13 H17 N O4'
_chemical_formula_weight         251.28
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2012-12-20
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 93.0379(10)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   8.89070(11)
_cell_length_b                   12.16463(14)
_cell_length_c                   12.12008(14)
_cell_measurement_reflns_used    9218
_cell_measurement_temperature    100(1)
_cell_measurement_theta_max      75.7059
_cell_measurement_theta_min      3.6305
_cell_volume                     1308.97(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
SHELXS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      100(1)
_diffrn_detector_area_resol_mean 8.3174
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
  1 omega   11.00   91.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       44.4841 -118.0000 -124.0000 80

  2 omega   66.00  111.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       44.4841   37.0000  -90.0000 45

  3 omega   21.00  116.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       44.4841   77.0000  -30.0000 95

  4 omega   30.00  110.00   1.0000    1.5000
omega____ theta____ kappa____ phi______ frames
    -       44.4841   37.0000   90.0000 80

  5 omega   34.00   65.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -30.0000   30.0000 31

  6 omega   42.00   93.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -94.0000   60.0000 51

  7 omega   34.00   67.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -30.0000 -120.0000 33

  8 omega   40.00   74.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -94.0000 -150.0000 34

  9 omega   50.00  143.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -15.0000  -90.0000 93

 10 omega   82.00  108.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -94.0000 -150.0000 26

 11 omega   35.00  119.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000 -125.0000   60.0000 84

 12 omega   90.00  178.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000   15.0000  150.0000 88

 13 omega   34.00   66.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -30.0000   60.0000 32

 14 omega   45.00  120.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000 -125.0000    0.0000 75

 15 omega   45.00  142.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -15.0000  120.0000 97

 16 omega   41.00   77.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -45.0000  -60.0000 36

 17 omega   41.00   90.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000 -125.0000 -180.0000 49

 18 omega   60.00  127.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -61.0000 -180.0000 67

 19 omega   36.00  121.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000 -125.0000 -150.0000 85

 20 omega   27.00   54.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -94.0000   90.0000 27

 21 omega   57.00  105.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -94.0000   90.0000 48

 22 omega   45.00   70.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      107.0000  -45.0000   60.0000 25
;
_diffrn_measurement_device_type  'Xcalibur, Onyx, Nova'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1180820000
_diffrn_orient_matrix_UB_12      0.0188946000
_diffrn_orient_matrix_UB_13      -0.0865895000
_diffrn_orient_matrix_UB_21      0.0340504000
_diffrn_orient_matrix_UB_22      -0.1242022000
_diffrn_orient_matrix_UB_23      -0.0009363000
_diffrn_orient_matrix_UB_31      -0.1221772000
_diffrn_orient_matrix_UB_32      -0.0162864000
_diffrn_orient_matrix_UB_33      -0.0934647000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0238
_diffrn_reflns_av_unetI/netI     0.0165
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            11312
_diffrn_reflns_theta_full        75.89
_diffrn_reflns_theta_max         75.89
_diffrn_reflns_theta_min         4.98
_diffrn_source                   'Nova (Cu) x-ray Source'
_exptl_absorpt_coefficient_mu    0.785
_exptl_absorpt_correction_T_max  1.894
_exptl_absorpt_correction_T_min  0.821
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET)
(compiled Jan 23 2012,18:06:46)
numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.275
_exptl_crystal_description       irregular
_exptl_crystal_F_000             536
_exptl_crystal_recrystallization_method hexane
_exptl_crystal_size_max          0.4157
_exptl_crystal_size_mid          0.3474
_exptl_crystal_size_min          0.1977
_refine_diff_density_max         0.358
_refine_diff_density_min         -0.188
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     165
_refine_ls_number_reflns         2689
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0381
_refine_ls_R_factor_gt           0.0362
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0510P)^2^+0.3960P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0934
_refine_ls_wR_factor_ref         0.0950
_reflns_number_gt                2547
_reflns_number_total             2689
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            ja4075997_si_002.cif
_cod_data_source_block           cs1945
_cod_database_code               4120781
_chemical_oxdiff_formula         'C13 H17 N O4'
_chemical_oxdiff_usercomment     'Zhenbin Niu/Stephen Craig (Duke) Niu-2-1'
_reflns_odcompleteness_completeness 99.40
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  {H4A,H4B} of C4, H3 of C3, H8 of C8, {H6A,H6B} of C6, {H7A,H7B} of C7, {H5A,
  H5B} of C5, H2 of C2
 At 1.5 times of:
  {H11A,H11B,H11C} of C11, {H13A,H13B,H13C} of C13
2.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C8(H8)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B)
2.c Idealised Me refined as rotating group:
 C11(H11A,H11B,H11C), C13(H13A,H13B,H13C)
;