Substituents Make a Difference: 6,6’’-modified Terpyridine Complexes with Helix Configuration and Enhanced Emission
Fu, Fan; Liu, Die; Zhao, Lili; Li, Huili; Bai, Xinyu; Chen, Mingzhao; Jiang, Zhilong; Su, Peiyang; Zhong, Wanying; Li, Yiming; Liao, Wei-Ming; He, Jun; Wang, Pingshan; Dalton Transactions  (2023) –; doi:10.1039/D2DT04006A

data_7712222
_publ_section_title
;
 Substituents Make a Difference: 6,6&#x2019;&#x2019;-modified Terpyridine
 Complexes with Helix Configuration and Enhanced Emission
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT04006A
_journal_year                    2023
_chemical_formula_moiety         'C70 H54 N6 Ni O4, 2(C F3 O3 S)'
_chemical_formula_sum            'C72 H54 F6 N6 Ni O10 S2'
_chemical_formula_weight         1400.04
_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   geom
_audit_creation_date             2022-05-03
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-11-16 deposited with the CCDC.	2023-01-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.098(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.0030(14)
_cell_length_b                   19.9002(11)
_cell_length_c                   17.2847(11)
_cell_measurement_reflns_used    4658
_cell_measurement_temperature    120.0(2)
_cell_measurement_theta_max      28.1520
_cell_measurement_theta_min      2.3660
_cell_volume                     6642.9(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.0(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5095
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -44.00  41.00   1.00   27.50    --   11.04 -77.00 150.00   85
  2  \w    -92.00 -63.00   1.00   27.50    --  -12.61   0.00 150.00   29
  3  \w     32.00  73.00   1.00   27.50    --  -12.61   0.00 150.00   41
  4  \w    -82.00  12.00   1.00   27.50    --  -12.61 -57.00 -30.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0220763000
_diffrn_orient_matrix_UB_12      0.0284530000
_diffrn_orient_matrix_UB_13      0.0071318000
_diffrn_orient_matrix_UB_21      -0.0291824000
_diffrn_orient_matrix_UB_22      0.0213096000
_diffrn_orient_matrix_UB_23      -0.0046025000
_diffrn_orient_matrix_UB_31      0.0027313000
_diffrn_orient_matrix_UB_32      -0.0025193000
_diffrn_orient_matrix_UB_33      0.0416862000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1337
_diffrn_reflns_av_unetI/netI     0.2109
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            31898
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.394
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.436
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93349
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.400
_exptl_crystal_description       needle
_exptl_crystal_F_000             2888
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.999
_refine_diff_density_min         -0.592
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     977
_refine_ls_number_reflns         11695
_refine_ls_number_restraints     543
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.2032
_refine_ls_R_factor_gt           0.0933
_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^)+(0.0705P)^2^+17.5605P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1899
_refine_ls_wR_factor_ref         0.2610
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5219
_reflns_number_total             11695
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt04006a2.cif
_cod_data_source_block           ld232-ni
_cod_database_code               7712222
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.958
_shelx_estimated_absorpt_t_min   0.945
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O1B-C32B \\sim O1-C32
 with sigma of 0.02
 C31B-C30 \\sim C31-C30
 with sigma of 0.02
 C32-C31 \\sim C31B-C32B
 with sigma of 0.02
 C33-C32 \\sim C33B-C32B
 with sigma of 0.02
 O1-C35 \\sim O1B-C35B
 with sigma of 0.02
 C33B-C34 \\sim C34-C33
 with sigma of 0.02
 O1-C33 \\sim O1-C31
 with sigma of 0.02
 O1B-C33B \\sim O1B-C31B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
S1 \\sim F1 \\sim F1A \\sim F2 \\sim F2A \\sim F3 \\sim F3A \\sim O3A \\sim O7
\\sim O8 \\sim O9 \\sim O10 \\sim O11 \\sim C43 \\sim C55: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
O1 \\sim C32 \\sim C35: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O1 \\sim O1B \\sim C29 \\sim C30 \\sim C31 \\sim C31B \\sim C32 \\sim C32B
\\sim C33 \\sim C33B \\sim C34 \\sim C35 \\sim C35B: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 S1, F1A, F2A, F3A, O3A, O10, O11, C55
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 S1, F1, F2, F3, O7, O8, O9, C43
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O1, C32, C35
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 C32
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O1, C29, C30, C31, C32, C33, C34, C35
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O1B, C29, C30, C31B, C32B, C33B, C34, C35B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(O3A)=Sof(O10)=Sof(O11)=Sof(C55)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(O7)=Sof(O8)=Sof(O9)=Sof(C43)=FVAR(1)
 Sof(O1B)=Sof(H34A)=Sof(H30B)=Sof(C31B)=Sof(H31B)=Sof(C32B)=Sof(C33B)=
 Sof(H33B)=Sof(C35B)=Sof(H35G)=Sof(H35H)=Sof(H35I)=1-FVAR(2)
 Sof(O1)=Sof(C31)=Sof(H31)=Sof(C32)=Sof(C33)=Sof(H33)=Sof(H34)=Sof(H30)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=FVAR(2)
6.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C1A(H1A), C2(H2), C2A(H2A), C3(H3), C3A(H3A), C5(H5), C5A(H5A),
 C6(H6), C6A(H6A), C8(H8), C8A(H8A), C10(H10), C10A(H10A), C13(H13), C13A(H13A),
  C14(H14), C14A(H14A), C15(H15), C15A(H15A), C18(H18), C18A(H18A), C19(H19),
 C19A(H19A), C21(H21), C21A(H21A), C22(H22), C22A(H22A), C25(H25), C25A(H25A),
 C26(H26), C26A(H26A), C27(H27), C27A(H27A), C30A(H30A), C31(H31), C33(H33),
 C34(H34), C34(H34A), C30(H30), C30(H30B), C31A(H31A), C31B(H31B), C33A(H33A),
 C33B(H33B), C34A(H34B)
6.b Fitted hexagon refined as free rotating group:
 C31(C32,C33,C34,C29,C30)
6.c Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C23A(H23D,H23E,H23F), C35(H35A,H35B,H35C), C35A(H35D,
 H35E,H35F), C35B(H35G,H35H,H35I)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              45330
_shelx_fab_checksum              4215
_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 1.122
_oxdiff_exptl_absorpt_empirical_full_min 0.921