Benzotrithiophene-based MOFs: interchromophoric interactions affected Ln(iii) crystallization selectivity and optoelectronic properties
Xie, Feng-Yang; Yang, Qi; Wang, Jia-Si; Yu, Hong-Yi; Li, Yue; Ruan, Wen-Juan; Dalton Transactions  (2021) –; doi:10.1039/D1DT02515E

data_7708844
_publ_section_title
;
 Benzotrithiophene-based MOFs: interchromophoric interactions affected
 Ln(iii) crystallization selectivity and optoelectronic properties
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D1DT02515E
_journal_year                    2021
_chemical_formula_moiety         'C72 H36 Tm6 O42 S15, 4(C2 H6 O S), 4(H2O)'
_chemical_formula_sum            'C80 H78 O50 S19 Tm6'
_chemical_formula_weight         3462.17
_space_group_crystal_system      monoclinic
_space_group_IT_number           12
_space_group_name_Hall           '-I 2y'
_space_group_name_H-M_alt        'I 1 2/m 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-10-11
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2021-10-25 deposited with the CCDC.	2021-11-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.549(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   15.0000(8)
_cell_length_b                   28.3529(10)
_cell_length_c                   17.0305(9)
_cell_measurement_reflns_used    7809
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      30.7110
_cell_measurement_theta_min      4.1290
_cell_volume                     6534.7(6)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.990
_diffrn_measured_fraction_theta_max 0.990
_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    -36.00  25.00   0.50   15.00    --   -1.00 -82.00   0.00  122
  2  \w    -19.00  84.00   0.50   15.00    --   -1.00  57.00 120.00  206
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0140604000
_diffrn_orient_matrix_UB_12      0.0012276000
_diffrn_orient_matrix_UB_13      0.0454365000
_diffrn_orient_matrix_UB_21      -0.0324287000
_diffrn_orient_matrix_UB_22      0.0193734000
_diffrn_orient_matrix_UB_23      -0.0068826000
_diffrn_orient_matrix_UB_31      -0.0386978000
_diffrn_orient_matrix_UB_32      -0.0157550000
_diffrn_orient_matrix_UB_33      -0.0047133000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0285
_diffrn_reflns_av_unetI/netI     0.0350
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            16084
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         3.830
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Mo) X-ray DW Source'
_exptl_absorpt_coefficient_mu    4.410
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61603
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_density_diffrn    1.759
_exptl_crystal_description       block
_exptl_crystal_F_000             2916
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_platon_squeeze_details
;
TITL 4778-2_a.res in P2(1)/n New:I2/m
CELL   15.0000   28.3529   17.0305     90.00    115.55     90.00
SPGR I2/m
Q101 0.745 0.345 0.136 !       8.98 eA-3
C102 0.500 0.125 0.003 !       6.09 eA-3
C103 1.000 0.141 0.000 !       2.25 eA-3
C104 0.301 0.496 0.281 !       2.19 eA-3
C105 0.514 0.821 0.047 !       2.18 eA-3
Q106 0.265 0.474 0.030 !       2.18 eA-3
C107 0.452 0.957 0.129 !       2.14 eA-3
Q108 0.531 0.981 0.218 !       2.11 eA-3
C109 0.327 0.502 0.234 !       2.05 eA-3
C110 0.475 0.845 0.045 !       1.82 eA-3
C111 0.935 0.498 0.359 !       1.68 eA-3
Q112 0.939 0.497 0.109 !       1.67 eA-3
C113 0.391 0.997 0.156 !       1.61 eA-3
Q114 0.673 0.442-0.004 !       1.59 eA-3
Q115 0.843 0.881 0.220 !       1.56 eA-3
Q116 0.697 0.679 0.142 !       1.52 eA-3
C117 0.037 0.109 0.058 !       1.46 eA-3
Q118 0.746 0.186 0.317 !       1.42 eA-3
Q119 0.878 0.485 0.044 !       1.38 eA-3
Q120 0.685 0.282 0.144 !       1.36 eA-3
Q121 0.739 1.001 0.266 !       1.33 eA-3
C122 1.000 0.078 0.003 !       1.32 eA-3
C123 0.454 0.094-0.010 !       1.29 eA-3
C124 0.545 0.162 0.103 !       1.28 eA-3
Q125 0.806 0.998 0.328 !       1.28 eA-3
Q126 0.356 0.474 0.020 !       1.26 eA-3
C127 0.136 0.967 0.170 !       1.24 eA-3
C128 1.000 0.102-0.010 !       1.23 eA-3
C129 0.096 0.928 0.097 !       1.19 eA-3
C130 0.140 0.929 0.061 !       1.16 eA-3
C131 0.106 0.023 0.229 !       1.15 eA-3
C132 0.606 0.523 0.729 !       1.15 eA-3
C133 0.169 1.003 0.156 !       1.14 eA-3
C134 0.449 1.005 0.094 !       1.13 eA-3
Q135 0.612 0.151 0.094 !       1.11 eA-3
C136 0.067 1.000 0.203 !       1.10 eA-3
Q137 0.738 0.305 0.135 !       1.09 eA-3
C138 0.426 0.113 0.017 !       1.07 eA-3
C139 0.919 0.033 0.797 !       1.07 eA-3
Q140 0.344 0.516 0.062 !       1.06 eA-3
C141 0.377 1.000 0.078 !       1.04 eA-3
Q142 0.569 0.018 0.296 !       1.01 eA-3
Q143 0.832 0.570 0.077 !       0.98 eA-3
Q144 0.924 0.484 0.047 !       0.94 eA-3
Q145 0.091 0.998 0.313 !       0.93 eA-3
Q146 0.830 0.898 0.154 !       0.90 eA-3
C147 0.106 1.006 0.172 !       0.90 eA-3
C148 0.018 0.921 0.122 !       0.90 eA-3
C149 0.785 1.001 0.047 !       0.88 eA-3
Q150 0.965 0.500 0.234 !       0.84 eA-3
Q151 0.572 0.846 0.066 !       0.84 eA-3
Q152 0.105 0.639 0.481 !       0.83 eA-3
Q153 0.804 0.157 0.232 !       0.82 eA-3
Q154 0.765 0.926 0.193 !       0.80 eA-3
C155 0.848 0.998 0.094 !       0.80 eA-3
C156 0.592 1.002 0.219 !       0.79 eA-3
Q157 0.017 0.547 0.154 !       0.77 eA-3
Q158 0.751 0.139 0.145 !       0.77 eA-3
Q159 0.654 0.698 0.084 !       0.77 eA-3
Q160 0.348 0.504 0.172 !       0.76 eA-3
C161 0.922 0.568 0.545 !       0.76 eA-3
C162 0.422 0.068 0.045 !       0.76 eA-3
Q163 0.441 0.655 0.188 !       0.75 eA-3
Q164 0.113 0.562 0.034 !       0.74 eA-3
Q165 0.082 0.538 0.057 !       0.73 eA-3
C166 0.036 0.985 0.144 !       0.72 eA-3
C167 0.595 0.052 0.966 !       0.71 eA-3
Q168 0.673 0.648 0.139 !       0.70 eA-3
C169 0.033 0.063 0.179 !       0.70 eA-3
Q170 0.685 1.001 0.484 !       0.70 eA-3
C171 0.500 0.521 0.330 !       0.70 eA-3
C172 0.035 0.057 0.103 !       0.69 eA-3
Q173 0.153 0.495 0.016 !       0.69 eA-3
C174 0.817 0.984 0.036 !       0.69 eA-3
C175 0.965 0.494 0.422 !       0.69 eA-3
Q176 0.632 0.702 0.188 !       0.68 eA-3
Q177 0.089 0.030 0.375 !       0.66 eA-3
C178 0.971 0.059 0.070 !       0.66 eA-3
Q179 0.576 0.968 0.214 !       0.65 eA-3
C180 0.142 0.461 0.480 !       0.65 eA-3
Q181 0.596 0.547 0.004 !       0.65 eA-3
C182 0.576 0.038 0.152 !       0.64 eA-3
Q183 0.906 0.765 0.320 !       0.64 eA-3
C184 0.859 0.442 0.530 !       0.64 eA-3
Q185 0.878 0.450 0.139 !       0.63 eA-3
Q186 0.422 0.501 0.078 !       0.63 eA-3
Q187 0.252 0.320 0.294 !       0.63 eA-3
Q188 0.829 0.344 0.173 !       0.62 eA-3
Q189 0.342 0.860 0.232 !       0.62 eA-3
C190 0.986 0.054 0.117 !       0.61 eA-3
Q191 0.844 0.838 0.422 !       0.61 eA-3
Q192 0.905 0.633 0.214 !       0.60 eA-3
Q193 0.824 0.531 0.111 !       0.60 eA-3
C194 0.495 0.115 0.112 !       0.60 eA-3
C195 0.318 0.974 0.027 !       0.60 eA-3
C196 0.689 0.963 0.018 !       0.60 eA-3
Q197 0.500 0.367 0.004 !       0.59 eA-3
Q198 0.773 0.635 0.312 !       0.59 eA-3
C199 0.027 1.002 0.078 !       0.59 eA-3
;
_refine_diff_density_max         6.408
_refine_diff_density_min         -1.850
_refine_diff_density_rms         0.158
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     469
_refine_ls_number_reflns         5836
_refine_ls_number_restraints     554
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0519
_refine_ls_R_factor_gt           0.0465
_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^)+(0.0606P)^2^+106.6891P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1199
_refine_ls_wR_factor_ref         0.1244
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5179
_reflns_number_total             5836
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02515e2.cif
_cod_data_source_block           4778-2_sq
_cod_original_formula_sum        'C80 H78 Tm6 O50 S19'
_cod_database_code               7708844
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.812
_shelx_estimated_absorpt_t_min   0.751
_reflns_odcompleteness_completeness 99.15
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Restrained distances
 S4-C18 = S4-C19
 1.8 with sigma of 0.02
 C19-C18
 2.7 with sigma of 0.04
 Tm1-O4 \\sim Tm1-O4A
 with sigma of 0.02
 C2-C1A \\sim C2A-C1A
 with sigma of 0.02
 Tm2-O1 \\sim Tm2-O1A
 with sigma of 0.02
 S2A-C14 \\sim S2A-C14A
 with sigma of 0.02
 S1A-C2 \\sim S1A-C2A
 with sigma of 0.02
 O2-C2 \\sim O2A-C2
 with sigma of 0.04
 C13A-C15 \\sim C13A-C15A
 with sigma of 0.04
 S3-C14 \\sim S3-C14A
 with sigma of 0.02
 C3A-C2 \\sim C3A-C2A
 with sigma of 0.02
 O5-C12 \\sim O5A-C12
 with sigma of 0.02
 O8-C17 \\sim O8A-C17A
 with sigma of 0.02
 O6-C12 \\sim O6A-C12
 with sigma of 0.02
 O8-O9 \\sim O8A-O9A
 with sigma of 0.04
 O1-C1 \\sim O1A-C1A
 with sigma of 0.02
 O3-C15 \\sim O3A-C15A
 with sigma of 0.02
 O1-C2 \\sim O1A-C2
 with sigma of 0.04
 O4-C15 \\sim O4A-C15A
 with sigma of 0.02
 C13-C15 \\sim C13-C15A
 with sigma of 0.04
 C13A-C14 \\sim C13A-C14A
 with sigma of 0.02
 S1-C2 \\sim S1-C2A
 with sigma of 0.02
 C14-C15 \\sim C14A-C15A
 with sigma of 0.02
 C3-C2 \\sim C3-C2A
 with sigma of 0.02
 C2-C1 \\sim C2-C1A
 with sigma of 0.02
 C2-C1 \\sim C2A-C1
 with sigma of 0.02
 Tm1-C15 \\sim Tm1-C15A
 with sigma of 0.04
 Tm1-O8 \\sim Tm1-O8A
 with sigma of 0.02
 Tm2-C1 \\sim Tm2-C1A
 with sigma of 0.04
 O9-C17 \\sim O9A-C17A
 with sigma of 0.02
 S3-C15 \\sim S3-C15A
 with sigma of 0.04
 Tm1-C17 \\sim Tm1-C17A
 with sigma of 0.04
 S2A-C15 \\sim S2A-C15A
 with sigma of 0.04
 O3-O4 \\sim O3A-O4A
 with sigma of 0.04
 O2-C1 \\sim O2A-C1A
 with sigma of 0.02
 O3-C14 \\sim O3A-C14A
 with sigma of 0.04
 C13-C14 \\sim C13-C14A
 with sigma of 0.02
 O4-C14 \\sim O4A-C14A
 with sigma of 0.04
 O1-O2 \\sim O1A-O2A
 with sigma of 0.04
 S4-O10 \\sim S4-O10A
 with sigma of 0.02
 Tm1-O10 \\sim Tm1-O10A
 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
S4 \\sim O10 \\sim C19 \\sim C18: within 3.8A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 3.8A
Uanis(S5) \\sim Ueq, Uanis(O11) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C19) \\sim Ueq, Uanis(C13A) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C10A)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C14) \\sim Ueq, Uanis(C14A) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.001
Uanis(C17) = Uanis(C17A)
Uanis(C1) = Uanis(C1A)
Uanis(O1) = Uanis(O1A)
Uanis(O9) = Uanis(O9A)
Uanis(O2) = Uanis(O2A)
Uanis(O8) = Uanis(O8A)
Uanis(C15) = Uanis(C15A)
Uanis(C14) = Uanis(C14A)
Uanis(O11A) = Uanis(O11)
Uanis(O11) = Uanis(O11A)
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(S2A)=Sof(S3A)=Sof(S1A)=Sof(C13A)=Sof(H13A)=Sof(C10A)=Sof(H10A)=Sof(C3A)=
 Sof(H3A)=Sof(O1A)=Sof(O2A)=Sof(C1A)=Sof(O5A)=Sof(O6A)=Sof(O3A)=Sof(O4A)=
 Sof(C14A)=Sof(C15A)=Sof(C2A)=1-FVAR(1)
 Sof(S3)=Sof(S2)=Sof(S1)=Sof(O3)=Sof(O4)=Sof(O5)=Sof(O6)=Sof(O1)=Sof(O2)=
 Sof(C13)=Sof(H13)=Sof(C10)=Sof(H10)=Sof(C3)=Sof(H3)=Sof(C14)=Sof(C15)=Sof(C2)=
 Sof(C1)=FVAR(1)
 Fixed Sof: S4(0.5) S5(0.25) O8(0.5) O9(0.5) O10(0.5) O11(0.25) C17(0.5)
 H17(0.5) C19(0.5) H19A(0.5) H19B(0.5) H19C(0.5) C18(0.5) H18A(0.5) H18B(0.5)
 H18C(0.5) C20(0.5) H20A(0.5) H20B(0.5) H20C(0.5) O8A(0.5) O9A(0.5) C17A(0.5)
 H17A(0.5) O11A(0.25) O10A(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C13(H13), C13A(H13A), C10(H10), C10A(H10A), C3(H3), C3A(H3A), C16(H16),
 C17(H17), C17A(H17A)
5.b Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C18(H18A,H18B,H18C), C20(H20A,H20B,H20C)
;
_platon_squeeze_void_probe_radius 1.20
_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 1.341
_oxdiff_exptl_absorpt_empirical_full_min 0.549