Deciphering the 3D Microstructures of a Doubly Charged Homopolymer through a Complementary Correlation of Monomer Crystallography and Polymer Powder X-ray Diffraction
Chen, Xi; Spiering, Glenn A.; Slebodnick, Carla; Long, Timothy E.; Moore, Robert B.; Macromolecules  (2020) –; doi:10.1021/acs.macromol.0c01270

data_1558695
_publ_section_title
;
 Deciphering the 3D Microstructures of a Doubly Charged Homopolymer
 through a Complementary Correlation of Monomer Crystallography and
 Polymer Powder X-ray Diffraction
;
_journal_name_full               Macromolecules
_journal_paper_doi               10.1021/acs.macromol.0c01270
_journal_year                    2020
_chemical_formula_moiety         '1.24(Br), 0.76(Cl), H2 O, C33 H58 N2'
_chemical_formula_sum            'C33 H60 Br1.24 Cl0.76 N2 O'
_chemical_formula_weight         626.86
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-10-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 93.864(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.70540(10)
_cell_length_b                   40.6996(9)
_cell_length_c                   12.4989(3)
_cell_measurement_reflns_used    14588
_cell_measurement_temperature    100.00(12)
_cell_measurement_theta_max      74.9640
_cell_measurement_theta_min      3.6800
_cell_volume                     3403.28(12)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(12)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.986
_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    -25.00  37.00   0.50    1.00    --  -42.55  19.00  60.00  124
  2  \w     -4.00  31.00   0.50    1.00    --  -42.55  38.00 -90.00   70
  3  \w    -43.00  -6.00   0.50    1.00    --  -42.55  38.00 -90.00   74
  4  \w    -54.00  31.00   0.50    1.00    --  -42.55  92.00 -26.00  170
  5  \w    -47.00 -16.00   0.50    4.00    --  -90.25  45.00   0.00   62
  6  \w    -74.00 -49.00   0.50    4.00    --  -90.25  92.00 -26.00   50
  7  \w    -51.00 -19.00   0.50    4.00    --  -90.25  45.00-180.00   64
  8  \w   -113.00 -86.00   0.50    1.00    --  -42.55 -77.00-180.00   54
  9  \w   -146.00-119.00   0.50    4.00    --  -90.25 -92.00-138.00   54
 10  \w   -116.00 -78.00   0.50    1.00    --  -42.55-125.00 -30.00   76
 11  \w   -116.00 -82.00   0.50    1.00    --  -42.55-125.00   0.00   68
 12  \w   -115.00 -89.00   0.50    1.00    --  -42.55 -77.00  90.00   52
 13  \w    -14.00  78.00   0.50    1.00    --   42.55 -92.00-138.00  184
 14  \w     85.00 115.00   0.50    1.00    --   42.55  77.00-120.00   60
 15  \w     99.00 138.00   0.50    4.00    --  111.75  92.00 -26.00   78
 16  \w    107.00 177.00   0.50    4.00    --  111.75  30.00  30.00  140
 17  \w    139.00 177.00   0.50    4.00    --  111.75  45.00   0.00   76
 18  \w    127.00 178.00   0.50    4.00    --  111.75  15.00 -30.00  102
 19  \w    130.00 178.00   0.50    4.00    --  111.75  15.00-120.00   96
 20  \w     84.00  94.00   0.50    4.00    --  111.75 -94.00-120.00   20
 21  \w     78.00  93.50   0.50    4.00    --  111.75 -92.00-138.00   31
 22  \w     40.00  71.00   0.50    4.00    --  111.75 -92.00-138.00   62
 23  \w     46.00 117.00   0.50    4.00    --  111.75-125.00-150.00  142
 24  \w     39.00  99.00   0.50    4.00    --  111.75 -77.00 -90.00  120
 25  \w     43.00 108.00   0.50    4.00    --  111.75-125.00-120.00  130
 26  \w     43.00 106.00   0.50    4.00    --  111.75-125.00 -60.00  126
 27  \w     38.00 109.00   0.50    4.00    --  111.75 -94.00 -30.00  142
 28  \w     41.00 116.00   0.50    4.00    --  111.75-125.00  90.00  150
 29  \w     58.00 116.00   0.50    4.00    --  111.75-125.00 150.00  116
 30  \w     39.00  66.00   0.50    4.00    --  111.75 -61.00   0.00   54
 31  \w     39.00 107.00   0.50    4.00    --  111.75 -94.00   0.00  136
 32  \w     38.00  72.00   0.50    4.00    --  111.75 -94.00-120.00   68
 33  \w     40.00 116.00   0.50    4.00    --  111.75-125.00-180.00  152
 34  \w     61.00 115.00   0.50    4.00    --  111.75  15.00 -30.00  108
 35  \w     91.00 126.00   0.50    4.00    --  111.75  45.00   0.00   70
 36  \w    100.00 178.00   0.50    4.00    --  111.75  45.00  90.00  156
 37  \w    143.00 169.00   0.50    4.00    --  111.75  30.00 120.00   52
 38  \w    107.00 135.00   0.50    4.00    --  111.75  30.00 120.00   56
 39  \w     38.00  71.00   0.50    4.00    --  111.75 -61.00  60.00   66
 40  \w     32.00  96.00   0.50    1.00    --   42.55-125.00  60.00  128
 41  \w     61.00 107.00   0.50    4.00    --  111.75  15.00-120.00   92
 42  \w     92.00 176.00   0.50    4.00    --  111.75 125.00-180.00  168
 43  \w     96.00 178.00   0.50    4.00    --  111.75 125.00-120.00  164
 44  \w    148.00 174.00   0.50    4.00    --  111.75  92.00 -26.00   52
 45  \w   -113.00 -85.00   0.50    1.00    --  -42.55-125.00-180.00   56
 46  \w   -116.00 -85.00   0.50    1.00    --  -42.55 -77.00 150.00   62
 47  \w     85.00 116.00   0.50    1.00    --   42.55  77.00  30.00   62
 48  \w    152.00 177.00   0.50    4.00    --  111.75  61.00  60.00   50
 49  \w    130.00 178.00   0.50    4.00    --  111.75  61.00  30.00   96
 50  \w    115.00 141.00   0.50    4.00    --  111.75 125.00  30.00   52
 51  \w     47.00  79.00   0.50    4.00    --  111.75-135.00  31.95   64
 52  \w    152.00 178.00   0.50    4.00    --  111.75 125.00  30.00   52
 53  \w     98.00 124.00   0.50    4.00    --  111.75-135.00  31.95   52
 54  \w     88.00 134.00   0.50    4.00    --  111.75  61.00  60.00   92
 55  \w     88.00 115.00   0.50    4.00    --  111.75  61.00  30.00   54
 56  \w    114.00 155.00   0.50    4.00    --  111.75  45.00  60.00   82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1728522000
_diffrn_orient_matrix_UB_12      0.0046165000
_diffrn_orient_matrix_UB_13      0.0737897000
_diffrn_orient_matrix_UB_21      -0.0784441000
_diffrn_orient_matrix_UB_22      -0.0345962000
_diffrn_orient_matrix_UB_23      -0.0301192000
_diffrn_orient_matrix_UB_31      0.1302540000
_diffrn_orient_matrix_UB_32      -0.0146640000
_diffrn_orient_matrix_UB_33      0.0944012000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0688
_diffrn_reflns_av_unetI/netI     0.0348
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       51
_diffrn_reflns_limit_k_min       -51
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            49748
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.460
_diffrn_reflns_theta_min         3.707
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.707
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.512
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53a (Rigaku Oxford Diffraction, 2019)
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    1.223
_exptl_crystal_description       plate
_exptl_crystal_F_000             1345
_exptl_crystal_recrystallization_method 'grown from CH3OH'
_exptl_crystal_size_max          0.202
_exptl_crystal_size_mid          0.112
_exptl_crystal_size_min          0.031
_refine_diff_density_max         0.784
_refine_diff_density_min         -1.014
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     404
_refine_ls_number_reflns         7161
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0584
_refine_ls_R_factor_gt           0.0511
_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^)+(0.0595P)^2^+3.9605P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1308
_refine_ls_wR_factor_ref         0.1354
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6189
_reflns_number_total             7161
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ma0c01270_si_002.cif
_cod_data_source_block           cs2557
_cod_database_code               1558695
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C33 H57 Br2 N2 H2 O'
_chemical_oxdiff_usercomment     'Xi Chen / TE Long (VBDC18BrCl)'
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All O(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Shared sites
{Br1, Cl1}
{Br2, Cl2}
3. Uiso/Uaniso restraints and constraints
Uanis(C9A) = Uanis(C9B)
Uanis(C13A) = Uanis(C13B)
Uanis(Br1) = Uanis(Cl1)
Uanis(Br2) = Uanis(Cl2)
4. Rigid body (RIGU) restrains
 C9A, C9B, C10A, C10B, C11A, C11B, C12A, C12B, C13A, C13B, C14A, C14B, C15A,
 C15B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C9B)=Sof(H9B)=Sof(C10B)=Sof(H10B)=Sof(C11B)=Sof(C12B)=Sof(H12B)=Sof(C13B)=
 Sof(H13B)=Sof(C14B)=Sof(H14B)=Sof(C15B)=Sof(H15C)=Sof(H15D)=1-FVAR(1)
 Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=Sof(C11A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=
 Sof(H13A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(H15B)=FVAR(1)
 Sof(Cl1)=1-FVAR(2)
 Sof(Br1)=FVAR(2)
 Sof(Cl2)=1-FVAR(3)
 Sof(Br2)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B),
 C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B),
  C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,
 H29B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B)
6.b Aromatic/amide H refined with riding coordinates:
 C9A(H9A), C9B(H9B), C10A(H10A), C10B(H10B), C12A(H12A), C12B(H12B),
 C13A(H13A), C13B(H13B), C14A(H14A), C14B(H14B)
6.c X=CH2 refined with riding coordinates:
 C15A(H15A,H15B), C15B(H15C,H15D)
6.d Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C)
;
_shelx_res_checksum              56297
_shelx_hkl_checksum              7665
_olex2_date_sample_data_collection 2019-10-11
_olex2_date_sample_submission    2019-09-26
_olex2_exptl_crystal_mounting_method 'Nylon loop with Paratone Oil'
_olex2_submission_original_sample_id VBDC18BrCl
_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 1.874
_oxdiff_exptl_absorpt_empirical_full_min 0.488