Reversible conformational switching of a photo-responsive <i>ortho</i>-azobenzene/2,6-pyridyldicarboxamide heterofoldamer.
Pike, Sarah J.; Telford, Richard; Male, Louise; Organic & biomolecular chemistry 21 (2023) 7717–7723; doi:10.1039/d3ob01137b

data_7159526
_publ_section_title
;
 Reversible conformational switching of a photo-responsive
 <i>ortho</i>-azobenzene/2,6-pyridyldicarboxamide heterofoldamer.
;
_journal_issue                   38
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              7717
_journal_page_last               7723
_journal_paper_doi               10.1039/d3ob01137b
_journal_volume                  21
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C59 H49 N9 O6, 1.5(C H Cl3)'
_chemical_formula_sum            'C60.5 H50.5 Cl4.5 N9 O6'
_chemical_formula_weight         1159.12
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-09
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2021-12-21 deposited with the CCDC.	2023-07-27 downloaded from the CCDC.
;
_cell_angle_alpha                68.486(3)
_cell_angle_beta                 74.716(3)
_cell_angle_gamma                88.134(2)
_cell_formula_units_Z            2
_cell_length_a                   10.3827(3)
_cell_length_b                   15.5971(4)
_cell_length_c                   19.3486(6)
_cell_measurement_reflns_used    19288
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      70.2560
_cell_measurement_theta_min      7.4470
_cell_volume                     2804.72(16)
_computing_cell_refinement       'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.982
_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    -89.00  89.00   0.25    0.40    --    0.00   0.00-180.00  712
  2  \w    -84.00  70.00   0.25    0.40    --    0.00  59.00 -30.00  616
  3  \w    -49.00 -22.00   0.25    1.60    --  -90.00  56.00  83.85  108
  4  \w    -68.00 -25.00   0.25    1.60    --  -90.00  55.00 -26.34  172
  5  \w   -164.00 -73.00   0.25    1.60    --  -90.00  49.00-150.00  364
  6  \w    -26.00  -1.00   0.25    1.60    --  -90.00  49.00-150.00  100
  7  \w    -98.00 -72.00   0.25    1.60    --  -90.00  30.00-180.00  104
  8  \w   -178.00-112.00   0.25    1.60    --  -90.00  59.00-124.94  264
  9  \w   -139.00 -83.00   0.25    1.60    --  -90.00  39.00  60.00  224
 10  \w   -166.00-132.00   0.25    1.60    --  -90.00  59.00  29.20  136
 11  \w   -103.00 -77.00   0.25    1.60    --  -90.00  59.00  29.20  104
 12  \w   -175.00-128.00   0.25    1.60    --  -90.00  59.00 -79.52  188
 13  \w    -77.00 -49.00   0.25    1.60    --  -90.00  59.00 -79.52  112
 14  \w   -178.00-151.00   0.25    1.60    --  -90.00  59.00 148.87  108
 15  \w   -142.00  -1.00   0.25    1.60    --  -90.00  59.00 148.87  564
 16  \w   -156.00-125.00   0.25    1.60    --  -90.00  30.00-180.00  124
 17  \w    -83.00 -51.00   0.25    1.60    --  -90.00  59.00-124.94  128
 18  \w   -163.00  -1.00   0.25    1.60    --  -90.00  10.00  60.00  648
 19  \w   -157.00 -97.00   0.25    1.60    --  -90.00  55.00 -26.34  240
 20  \w   -140.00 -54.00   0.25    1.60    --  -90.00  56.00  83.85  344
 21  \w   -178.00 -16.00   0.25    1.60    --  -90.00  59.00 109.17  648
 22  \w   -178.00-110.00   0.25    1.60    --  -90.00  30.00 -60.00  272
 23  \w    -66.00  -1.00   0.25    1.60    --  -90.00  30.00 -60.00  260
 24  \w   -178.00 -90.00   0.25    1.60    --  -90.00  59.00  -9.83  352
 25  \w   -178.00 -90.00   0.25    1.60    --  -90.00  54.00 -78.38  352
 26  \w   -176.00-151.00   0.25    1.60    --  -90.00  59.00-160.27  100
 27  \w   -165.00-140.00   0.25    1.60    --  -90.00  59.00 120.80  100
 28  \w   -179.00-147.00   0.25    1.60    --  -90.00  56.00  83.85  128
 29  \w   -178.00-153.00   0.25    1.60    --  -90.00  59.00-124.94  100
 30  \w    -89.00  89.00   0.25    0.40    --    0.00  49.00 -90.00  712
 31  \w    -89.00  89.00   0.25    0.40    --    0.00  59.00 150.00  712
 32  \w    -89.00  89.00   0.25    0.40    --    0.00  20.00 -60.00  712
 33  \w    -89.00  89.00   0.25    0.40    --    0.00  59.00  30.00  712
 34  \w   -179.00  -1.00   0.25    1.60    --  -90.00  58.00   5.91  712
 35  \w   -179.00 -51.00   0.25    1.60    --  -90.00  59.00 -88.77  512
 36  \w   -179.00  -1.00   0.25    1.60    --  -90.00   0.00-120.00  712
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0295073000
_diffrn_orient_matrix_UB_12      -0.0122829000
_diffrn_orient_matrix_UB_13      0.0855322000
_diffrn_orient_matrix_UB_21      0.0451800000
_diffrn_orient_matrix_UB_22      0.1023787000
_diffrn_orient_matrix_UB_23      -0.0242376000
_diffrn_orient_matrix_UB_31      -0.1444626000
_diffrn_orient_matrix_UB_32      0.0264103000
_diffrn_orient_matrix_UB_33      0.0006348000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            30674
_diffrn_reflns_point_group_measured_fraction_full 0.804
_diffrn_reflns_point_group_measured_fraction_max 0.799
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.453
_diffrn_reflns_theta_min         2.550
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.634
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91463
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.118a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.373
_exptl_crystal_description       plate
_exptl_crystal_F_000             1202
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.025
_refine_diff_density_max         0.566
_refine_diff_density_min         -0.451
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.019(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1548
_refine_ls_number_reflns         30674
_refine_ls_number_restraints     202
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.0661
_refine_ls_R_factor_gt           0.0627
_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^)+(0.1184P)^2^+1.3753P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1733
_refine_ls_wR_factor_ref         0.1767
_reflns_Friedel_coverage         0.626
_reflns_Friedel_fraction_full    0.621
_reflns_Friedel_fraction_max     0.615
_reflns_number_gt                28684
_reflns_number_total             30674
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -178.9512\% 
around [0.89 0.00 0.45] (reciprocal) or [1.00 -0.03 0.01] (direct)
;
_cod_data_source_file            d3ob01137b2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7159526--7159527.cif.'
_cod_original_cell_volume        2804.72(15)
_cod_original_formula_sum        'C60.50 H50.50 Cl4.50 N9 O6'
_cod_database_code               7159526
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C59 H49 N9 O6'
_chemical_oxdiff_usercomment     'SP417c '
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.468
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.4476(11)
 0.5524(11)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C401-Cl42 = C401-Cl43 = C401-Cl41
 1.78 with sigma of 0.02
 C41B-Cl2B = C41B-Cl3B = C41B-Cl1B
 1.78 with sigma of 0.02
 C31A-Cl1A = C31A-Cl3A = C31A-Cl2A
 1.78 with sigma of 0.02
 C301-Cl31 = C301-Cl33 = C301-Cl32
 1.78 with sigma of 0.02
 N2-H2A = N5-H5 = N6-H6 = N9-H9A = N102-H10A = N106-H106 = N109-H10B
 0.88 with sigma of 0.02
 Cl2B-Cl3B \\sim Cl3B-Cl1B \\sim Cl1B-Cl2B
 with sigma of 0.04
 C401-Cl42 \\sim C401-Cl43 \\sim C401-Cl41
 with sigma of 0.02
 Cl42-Cl43 \\sim Cl43-Cl41 \\sim Cl41-Cl42
 with sigma of 0.04
 C41B-Cl2B \\sim C41B-Cl3B \\sim C41B-Cl1B
 with sigma of 0.02
 Cl1A-Cl3A \\sim Cl3A-Cl2A \\sim Cl2A-Cl1A
 with sigma of 0.04
 C301-Cl31 \\sim C301-Cl33 \\sim C301-Cl32
 with sigma of 0.02
 C31A-Cl1A \\sim C31A-Cl3A \\sim C31A-Cl2A
 with sigma of 0.02
 Cl31-Cl33 \\sim Cl33-Cl32 \\sim Cl32-Cl31
 with sigma of 0.04
4. Rigid bond restraints
 C301, Cl31, Cl32, Cl33, C31A, Cl1A, Cl2A, Cl3A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C401, Cl41, Cl42, Cl43, C41B, Cl1B, Cl2B, Cl3B
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Uiso/Uaniso restraints and constraints
C301 \\sim C31A \\sim Cl31 \\sim Cl32 \\sim Cl33 \\sim C31A \\sim Cl1A \\sim
Cl2A \\sim Cl3A: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.01 within 1.7A
C401 \\sim C41B \\sim Cl41 \\sim Cl42 \\sim Cl43 \\sim C41B \\sim Cl1B \\sim
Cl2B \\sim Cl3B: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.01 within 1.7A
6. Rigid body (RIGU) restrains
 C401, Cl41, Cl42, Cl43
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C41B, Cl1B, Cl2B, Cl3B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C31A, Cl1A, Cl2A, Cl3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C301, Cl31, Cl32, Cl33
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(C31A)=Sof(H31A)=Sof(Cl1A)=Sof(Cl2A)=Sof(Cl3A)=1-FVAR(1)
 Sof(C301)=Sof(H301)=Sof(Cl31)=Sof(Cl32)=Sof(Cl33)=FVAR(1)
 Sof(C41B)=Sof(H41B)=Sof(Cl1B)=Sof(Cl2B)=Sof(Cl3B)=1-FVAR(2)
 Sof(C401)=Sof(H401)=Sof(Cl41)=Sof(Cl42)=Sof(Cl43)=FVAR(2)
8.a Ternary CH refined with riding coordinates:
 C20(H20), C47(H47), C120(H120), C147(H147), C201(H201), C301(H301),
 C31A(H31A), C401(H401), C41B(H41B)
8.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C9(H9), C10(H10), C11(H11), C12(H12), C15(H15),
 C16(H16), C17(H17), C18(H18), C23(H23), C25(H25), C26(H26), C28(H28), C30(H30),
  C31(H31), C36(H36), C37(H37), C38(H38), C39(H39), C42(H42), C43(H43),
 C44(H44), C45(H45), C50(H50), C52(H52), C53(H53), C55(H55), C57(H57), C58(H58),
  C102(H102), C103(H103), C104(H104), C109(H109), C110(H110), C111(H111),
 C112(H112), C115(H115), C116(H116), C117(H117), C118(H118), C123(H123),
 C125(H125), C126(H126), C128(H128), C130(H130), C131(H131), C136(H136),
 C137(H137), C138(H138), C139(H139), C142(H142), C143(H143), C144(H144),
 C145(H145), C150(H150), C152(H152), C153(H153), C155(H155), C157(H157),
 C158(H158)
8.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C32(H32A,H32B,H32C), C48(H48A,H48B,H48C), C59(H59A,H59B,
 H59C), C121(H12A,H12B,H12C), C132(H13A,H13B,H13C), C148(H14A,H14B,H14C),
 C159(H15A,H15B,H15C)
;
_shelx_res_checksum              78426
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.521
_oxdiff_exptl_absorpt_empirical_full_min 0.676
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2