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_7708842
_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 Er6 O42 S15, 4(C2 H6 O S), 4(H2O)'
_chemical_formula_sum            'C80 H78 Er6 O50 S19'
_chemical_formula_weight         3452.15
_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                 115.635(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   15.0482(4)
_cell_length_b                   28.3988(5)
_cell_length_c                   17.0500(5)
_cell_measurement_reflns_used    18883
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      30.5120
_cell_measurement_theta_min      3.6960
_cell_volume                     6569.1(3)
_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 2014/5 (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    -19.00  26.00   0.50    1.58    --   -1.10 -82.00   0.00   90
  2  \w    -76.00 -15.00   0.50    1.58    --    1.10 -38.00   0.00  122
  3  \w     -1.00  65.00   0.50    1.58    --    1.10  38.00 150.00  132
;
_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      -0.0302419000
_diffrn_orient_matrix_UB_12      0.0184741000
_diffrn_orient_matrix_UB_13      0.0028768000
_diffrn_orient_matrix_UB_21      -0.0185170000
_diffrn_orient_matrix_UB_22      -0.0152397000
_diffrn_orient_matrix_UB_23      0.0223898000
_diffrn_orient_matrix_UB_31      0.0383775000
_diffrn_orient_matrix_UB_32      0.0071479000
_diffrn_orient_matrix_UB_33      0.0402348000
_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  0.0226
_diffrn_reflns_av_unetI/netI     0.0275
_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       17
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            16669
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         3.738
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Mo) X-ray DW Source'
_exptl_absorpt_coefficient_mu    4.168
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67716
_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 purple'
_exptl_crystal_density_diffrn    1.745
_exptl_crystal_description       block
_exptl_crystal_F_000             2902
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.14
_platon_squeeze_details
;
TITL er_a.res in I2/m
CELL   15.0482   28.3988   17.0500     90.00    115.64     90.00
SPGR I2/m
Q101 0.747 0.659 0.146 !       8.20 eA-3
C102 0.500 0.125 0.006 !       5.92 eA-3
Q103 0.236 0.025 0.473 !       2.81 eA-3
Q104 0.328 0.552 0.019 !       2.64 eA-3
C105 1.000 0.141-0.003 !       2.31 eA-3
Q106 0.355 0.476 0.019 !       2.28 eA-3
Q107 0.690 0.681 0.124 !       2.16 eA-3
C108 0.189 1.001 0.234 !       2.07 eA-3
Q109 0.905 0.483 0.095 !       2.04 eA-3
Q110 0.532 0.980 0.218 !       1.93 eA-3
C111 0.467 0.950 0.146 !       1.86 eA-3
C112 0.489 0.153 0.065 !       1.84 eA-3
C113 0.511 0.822 0.028 !       1.80 eA-3
Q114 0.737 0.296 0.143 !       1.73 eA-3
C115 0.397 0.998 0.156 !       1.70 eA-3
Q116 0.842 0.113 0.217 !       1.70 eA-3
C117 0.460 1.004 0.109 !       1.67 eA-3
C118 0.413 1.002 0.125 !       1.65 eA-3
Q119 0.665 0.712 0.143 !       1.53 eA-3
C120 0.032 0.100 0.069 !       1.53 eA-3
C121 0.988 0.913 0.010 !       1.44 eA-3
C122 0.588 1.000 0.156 !       1.39 eA-3
C123 1.000 0.109-0.001 !       1.34 eA-3
Q124 0.750 0.311 0.182 !       1.31 eA-3
C125 0.748 0.498 0.234 !       1.31 eA-3
C126 0.442 0.090 0.003 !       1.30 eA-3
C127 0.361 1.002 0.063 !       1.28 eA-3
C128 0.388 0.569 0.444 !       1.28 eA-3
Q129 0.769 0.061 0.187 !       1.19 eA-3
Q130 0.673 0.604 0.345 !       1.19 eA-3
C131 0.397 0.960 0.119 !       1.16 eA-3
Q132 0.666 0.506 0.141 !       1.15 eA-3
Q133 0.129 0.445 0.032 !       1.12 eA-3
C134 0.125 0.044 0.168 !       1.11 eA-3
Q135 0.551 0.013 0.282 !       1.11 eA-3
Q136 0.405 0.502 0.187 !       1.10 eA-3
Q137 0.628 0.301 0.185 !       1.04 eA-3
C138 0.412 0.505 0.250 !       1.02 eA-3
Q139 0.883 0.446 0.158 !       1.02 eA-3
C140 0.410 1.006 0.062 !       1.01 eA-3
Q141 0.449 0.448 0.092 !       0.99 eA-3
C142 0.419 0.463 0.304 !       0.97 eA-3
Q143 0.081 0.531 0.051 !       0.97 eA-3
Q144 0.347 0.499 0.078 !       0.97 eA-3
Q145 0.609 0.853 0.090 !       0.94 eA-3
C146 0.500 0.086 0.010 !       0.94 eA-3
C147 0.347 0.511 0.347 !       0.93 eA-3
C148 0.076 1.003 0.156 !       0.93 eA-3
Q149 0.738 0.860 0.121 !       0.92 eA-3
Q150 0.834 0.428 0.075 !       0.89 eA-3
Q151 0.882 0.599 0.153 !       0.85 eA-3
C152 0.338 0.961 0.018 !       0.85 eA-3
Q153 0.665 0.359 0.106 !       0.84 eA-3
C154 0.428 0.879 0.032 !       0.83 eA-3
Q155 0.128 0.428 0.121 !       0.83 eA-3
C156 0.319 0.968 0.125 !       0.82 eA-3
C157 0.288 0.999 0.094 !       0.82 eA-3
C158 0.196 0.476 0.452 !       0.82 eA-3
Q159 0.630 0.467 0.060 !       0.81 eA-3
Q160 0.098 0.543 0.077 !       0.81 eA-3
Q161 0.720 0.127 0.173 !       0.80 eA-3
Q162 0.334 0.499 0.109 !       0.80 eA-3
Q163 0.070 0.538 0.125 !       0.80 eA-3
C164 0.070 0.064 0.001 !       0.79 eA-3
C165 0.044 0.054 0.167 !       0.79 eA-3
Q166 0.814 0.463 0.113 !       0.78 eA-3
C167 0.084 0.057 0.117 !       0.77 eA-3
Q168 0.667 0.115 0.333 !       0.75 eA-3
Q169 0.018 0.445 0.158 !       0.75 eA-3
Q170 0.853 0.855 0.111 !       0.74 eA-3
C171 0.133 0.499 0.484 !       0.73 eA-3
C172 0.275 0.018 0.156 !       0.73 eA-3
Q173 0.893 0.634 0.206 !       0.73 eA-3
C174 0.019 0.912 0.167 !       0.72 eA-3
C175 0.606 1.004 0.219 !       0.72 eA-3
C176 0.518 0.584 0.646 !       0.72 eA-3
C177 0.045 0.057 0.134 !       0.72 eA-3
C178 0.530 0.561 0.438 !       0.70 eA-3
Q179 0.439 0.341 0.201 !       0.68 eA-3
Q180 0.044 0.564 0.110 !       0.67 eA-3
C181 0.376 0.052 0.031 !       0.67 eA-3
C182 0.776 0.471 0.485 !       0.67 eA-3
Q183 0.793 0.282 0.171 !       0.67 eA-3
Q184 0.871 0.766 0.378 !       0.64 eA-3
Q185 0.767 0.044 0.250 !       0.64 eA-3
Q186 0.829 0.421 0.138 !       0.62 eA-3
C187 0.530 0.129 0.125 !       0.61 eA-3
Q188 0.700 0.131 0.312 !       0.60 eA-3
Q189 0.339 0.028 0.202 !       0.58 eA-3
Q190 0.364 0.049 0.139 !       0.58 eA-3
Q191 0.253 0.405 0.153 !       0.57 eA-3
Q192 0.713 0.323 0.079 !       0.57 eA-3
Q193 0.857 0.998 0.125 !       0.56 eA-3
C194 0.729 0.028 0.048 !       0.56 eA-3
C195 0.298 0.462 0.462 !       0.56 eA-3
Q196 0.989 0.537 0.128 !       0.56 eA-3
C197 0.213 0.969 0.194 !       0.55 eA-3
Q198 0.829 0.666 0.155 !       0.55 eA-3
Q199 0.220 0.133 0.314 !       0.54 eA-3
;
_refine_diff_density_max         6.186
_refine_diff_density_min         -2.010
_refine_diff_density_rms         0.166
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     457
_refine_ls_number_reflns         5869
_refine_ls_number_restraints     595
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0556
_refine_ls_R_factor_gt           0.0525
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0515P)^2^+167.0269P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1283
_refine_ls_wR_factor_ref         0.1308
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5446
_reflns_number_total             5869
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1dt02515e2.cif
_cod_data_source_block           er_sq
_cod_database_code               7708842
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 98.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Restrained distances
 S5-C19 = S5-C18
 1.8 with sigma of 0.02
 S4-C20
 1.8 with sigma of 0.02
 S3A-C2 \\sim S3A-C2A
 with sigma of 0.02
 O1-C14 \\sim O1A-C14A
 with sigma of 0.04
 C13A-C15 \\sim C13A-C15A
 with sigma of 0.04
 S3-C2 \\sim S3-C2A
 with sigma of 0.02
 O6-C2 \\sim O6A-C2A
 with sigma of 0.04
 O1-C15 \\sim O1A-C15A
 with sigma of 0.02
 Er1-O10 \\sim Er1-O10A
 with sigma of 0.02
 O2-C15 \\sim O2A-C15A
 with sigma of 0.02
 S1A-C14 \\sim S1A-C14A
 with sigma of 0.02
 Er1-O8 \\sim Er1-O8A
 with sigma of 0.02
 Er2-O5 \\sim Er2-O5A
 with sigma of 0.02
 C3A-C1 \\sim C3A-C1A
 with sigma of 0.04
 S1-C15 \\sim S1-C15A
 with sigma of 0.04
 Er1-O2 \\sim Er1-O2A
 with sigma of 0.02
 S3-C1 \\sim S3-C1A
 with sigma of 0.04
 O5-O6 \\sim O5A-O6A
 with sigma of 0.04
 S1A-C15 \\sim S1A-C15A
 with sigma of 0.04
 S1-C14 \\sim S1-C14A
 with sigma of 0.02
 S3A-C1 \\sim S3A-C1A
 with sigma of 0.04
 O8-C17 \\sim O8A-C17A
 with sigma of 0.02
 O1-O2 \\sim O1A-O2A
 with sigma of 0.04
 O9-C17 \\sim O9A-C17A
 with sigma of 0.02
 O2-C14 \\sim O2A-C14A
 with sigma of 0.04
 C13A-C14 \\sim C13A-C14A
 with sigma of 0.02
 O5-C2 \\sim O5A-C2A
 with sigma of 0.04
 C13-C14 \\sim C13-C14A
 with sigma of 0.02
 O8-O9 \\sim O8A-O9A
 with sigma of 0.04
 C3A-C2 \\sim C3A-C2A
 with sigma of 0.02
 C3-C2 \\sim C3-C2A
 with sigma of 0.02
 C13-C15 \\sim C13-C15A
 with sigma of 0.04
 C14-C15 \\sim C14A-C15A
 with sigma of 0.02
 C3-C1 \\sim C3-C1A
 with sigma of 0.04
 C2-C1 \\sim C2A-C1A
 with sigma of 0.02
 S5-O10 \\sim S5-O10A
 with sigma of 0.02
 O5-C1 \\sim O5A-C1A
 with sigma of 0.02
 Er1-C15 \\sim Er1-C15A
 with sigma of 0.04
 O6-C1 \\sim O6A-C1A
 with sigma of 0.02
 Er1-C17 \\sim Er1-C17A
 with sigma of 0.04
 Er2-C1 \\sim Er2-C1A
 with sigma of 0.04
2. Restrained planarity
 S1, C13, C7, C14, C15, C6, C8, C9, C4, C5
 with sigma of 0.1
3. Uiso/Uaniso restraints and constraints
S5 \\sim O10 \\sim C18 \\sim C19: within 3.8A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 3.8A
C20 \\sim S4 \\sim O11: within 3.8A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 3.8A
Uanis(S4) \\sim Ueq, Uanis(O11) \\sim Ueq, Uanis(C20) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C18) \\sim Ueq, Uanis(O8) \\sim Ueq, Uanis(O9) \\sim Ueq, Uanis(C13)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C13A) \\sim Ueq, Uanis(C10) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(O2) \\sim Ueq, Uanis(O2A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.01
Uanis(C14) \\sim Ueq, Uanis(C14A) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.005
Uanis(O1) = Uanis(O1A)
Uanis(C15) = Uanis(C15A)
Uanis(O2) = Uanis(O2A)
Uanis(O5) = Uanis(O5A)
Uanis(O6) = Uanis(O6A)
Uanis(C14) = Uanis(C14A)
Uanis(O10) = Uanis(O10A)
Uanis(O11A) = Uanis(O11)
4. 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
5. Others
 Sof(S1A)=Sof(S2A)=Sof(S3A)=Sof(C13A)=Sof(H13A)=Sof(C10A)=Sof(H10A)=Sof(C3A)=
 Sof(H3A)=Sof(O1A)=Sof(O2A)=Sof(C15A)=Sof(O5A)=Sof(O6A)=Sof(C2A)=Sof(C1A)=
 Sof(C14A)=1-FVAR(1)
 Sof(S1)=Sof(S2)=Sof(S3)=Sof(O1)=Sof(O2)=Sof(O5)=Sof(O6)=Sof(C13)=Sof(H13)=
 Sof(C10)=Sof(H10)=Sof(C3)=Sof(H3)=Sof(C14)=Sof(C15)=Sof(C2)=Sof(C1)=FVAR(1)
 Fixed Sof: S5(0.5) S4(0.25) O8(0.5) O9(0.5) O10(0.5) O11(0.25) H16(0.25)
 C17(0.5) H17(0.5) C18(0.5) H18A(0.5) H18B(0.5) H18C(0.5) C19(0.5) H19A(0.5)
 H19B(0.5) H19C(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) O10A(0.5) O11A(0.25)
6.a Aromatic/amide H refined with riding coordinates:
 C13A(H13A), C13(H13), C10A(H10A), C10(H10), C3A(H3A), C3(H3), C16(H16),
 C17(H17), C17A(H17A)
6.b Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), 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 1.558
_oxdiff_exptl_absorpt_empirical_full_min 0.747