Coordinative-to-Covalent Transformation, Isomerization Dynamics, and Logic Gate Application of Dithienylethene Based Photochromic Cages
Zhang, Jianhua; Wang, Hai-Ping; Zhang, Lu-Yin; Wei, Shi-Chao; Wei, Zhang-Wen; Pan, Mei; Su, Cheng-Yong; Chemical Science  (2020) –; doi:10.1039/D0SC03290E

data_1558814
_publ_section_title
;
 Coordinative-to-Covalent Transformation, Isomerization Dynamics, and
 Logic Gate Application of Dithienylethene Based Photochromic Cages
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC03290E
_journal_year                    2020
_chemical_formula_moiety
'C99 H102 Cd2 N14 S6, 4(C F3 O3 S), 3(C2 H3 N)'
_chemical_formula_sum            'C109 H111 Cd2 F12 N17 O12 S10'
_chemical_formula_weight         2624.54
_chemical_name_common            A2L3Cd2
_chemical_properties_physical    Efflorescent,Light-sensitive
_space_group_crystal_system      tetragonal
_space_group_IT_number           96
_space_group_name_Hall           'P 4nw 2abw'
_space_group_name_H-M_alt        'P 43 21 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-20
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-05-20 deposited with the CCDC.	2020-08-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.54180(10)
_cell_length_b                   13.54180(10)
_cell_length_c                   66.0707(8)
_cell_measurement_reflns_used    12135
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      71.4630
_cell_measurement_theta_min      3.5100
_cell_volume                     12116.07(19)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6525
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.984
_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    -74.00 -35.75   0.75    8.00    --  -41.14  89.00  41.00   51
  2  \w      9.00  34.50   0.75    8.00    --   41.14 -89.00 -73.00   34
  3  \w    115.00 141.25   0.75   30.00    --  106.40  89.00  41.00   35
  4  \w     24.00  92.25   0.75   30.00    --  106.40 -89.00 -73.00   91
  5  \w   -128.00 -38.75   0.75    8.00    --  -41.14 178.00  30.00  119
  6  \w     94.00 178.00   0.75   30.00    --  106.40 125.00 -60.00  112
  7  \w     94.00 131.50   0.75   30.00    --  106.40 125.00   0.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0234706000
_diffrn_orient_matrix_UB_12      0.0509570000
_diffrn_orient_matrix_UB_13      -0.0202899000
_diffrn_orient_matrix_UB_21      -0.1101707000
_diffrn_orient_matrix_UB_22      0.0039989000
_diffrn_orient_matrix_UB_23      0.0057645000
_diffrn_orient_matrix_UB_31      0.0160473000
_diffrn_orient_matrix_UB_32      0.1016255000
_diffrn_orient_matrix_UB_33      0.0099388000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0435
_diffrn_reflns_av_unetI/netI     0.0407
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       74
_diffrn_reflns_limit_l_min       -81
_diffrn_reflns_number            33381
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.446
_diffrn_reflns_theta_min         3.331
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.122
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.23981
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.439
_exptl_crystal_description       plate
_exptl_crystal_F_000             5376
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         4.608
_refine_diff_density_min         -1.944
_refine_diff_density_rms         0.146
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.13(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     756
_refine_ls_number_reflns         11878
_refine_ls_number_restraints     302
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.1046
_refine_ls_R_factor_gt           0.0978
_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^)+(0.1688P)^2^+51.3190P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2610
_refine_ls_wR_factor_ref         0.2706
_reflns_Friedel_coverage         0.731
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.982
_reflns_number_gt                10831
_reflns_number_total             11878
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc03290e2.cif
_cod_data_source_block           exp_2090
_cod_original_cell_volume        12116.1(2)
_cod_database_code               1558814
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.514
_shelx_estimated_absorpt_t_min   0.514
_reflns_odcompleteness_completeness 97.60
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.87(2)
 0.13(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 N9-C56
 1.1 with sigma of 0.001
 C35-H35B = C35-H35A = C35-H35C = C35-H35D
 0.99 with sigma of 0.001
 H35B-C34 = H35A-C34 = H35C-C34 = H35D-C34
 2.046 with sigma of 0.01
 H35B-C36 = H35A-C36
 2.092 with sigma of 0.01
 H35B-H35A = H35C-H35D
 1.611 with sigma of 0.01
 C36-H36A = C36-H36B
 0.99 with sigma of 0.001
 H36A-C35 = H36B-C35
 2.092 with sigma of 0.01
 H36A-H36B
 1.611 with sigma of 0.01
 S5-O5 = S5-O6 = S5-O4 = S4-O1 = S4-O3 = S4-O2
 1.43 with sigma of 0.01
 F2-C51 = F3-C51 = F1-C51 = F5-C52 = F6-C52 = F4-C52
 1.34 with sigma of 0.01
 S5-C52 = S4-C51
 1.75 with sigma of 0.01
 O1-C51 = O2-C51 = O3-C51 = O4-C52 = O5-C52 = O6-C52
 2.51 with sigma of 0.01
 F1-S4 = F2-S4 = F3-S4 = F4-S5 = F5-S5 = F6-S5
 2.6 with sigma of 0.01
 C55-C56
 1.42 with sigma of 0.001
 N9-C55
 2.52 with sigma of 0.001
 C14-C13
 1.519 with sigma of 0.001
 S1-C13
 1.753 with sigma of 0.001
 S1-C10
 1.781 with sigma of 0.001
 C33-C32
 1.536 with sigma of 0.001
 S2-C32
 1.762 with sigma of 0.001
 S2-C29
 1.737 with sigma of 0.001
 C32-C31
 1.366 with sigma of 0.001
 C31-C30
 1.416 with sigma of 0.001
 C30-C29
 1.339 with sigma of 0.001
 F1-F2 \\sim F2-F3 \\sim F3-F1 \\sim F4-F5 \\sim F5-F6 \\sim F6-F4
 with sigma of 0.02
 O1-O2 \\sim O2-O3 \\sim O3-O1 \\sim O4-O5 \\sim O5-O6 \\sim O6-O4
 with sigma of 0.02
4. Rigid bond restraints
 C10, S1, C13, C12, C11
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O6, S5, O4, O5, C52, F5, F4, F6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F3, C51, F2, F1, O1, S4, O2, O3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C29, C32, C31, C30, S2, C33
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
S1 \\sim C13 \\sim C12 \\sim C11 \\sim C10: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
F6 \\sim F5 \\sim C52 \\sim F4 \\sim O4 \\sim S5 \\sim O6 \\sim O5: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
O2 \\sim S4 \\sim O3 \\sim O1 \\sim C51 \\sim F3 \\sim F2 \\sim F1: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
C33 \\sim C32 \\sim C31 \\sim C30 \\sim C29 \\sim S2: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(S2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N9) = Uanis(C56) = Uanis(C55)
6. Others
 Fixed Sof: N9(0.5) H35C(0.5) H35D(0.5) H35A(0.5) H35B(0.5) C36(0.5) H36A(0.5)
 C55(0.5) H55A(0.5) H55B(0.5) H55C(0.5) C56(0.5)
7.a Riding coordinates:
 C33(H33A,H33B,H33C), C55(H55A,H55B,H55C)
7.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C17(H17A,H17B), C18(H18A,H18B),
 C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C37(H37A,H37B),
  C38(H38A,H38B), C39(H39A,H39B)
7.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C6(H6), C7(H7), C9(H9), C11(H11), C23(H23), C25(H25), C26(H26),
 C28(H28), C30(H30), C40(H40), C42(H42), C43(H43), C45(H45), C47(H47)
7.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C50(H50A,H50B,H50C), C53(H53A,H53B,H53C)
;
_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 3.021
_oxdiff_exptl_absorpt_empirical_full_min 0.706