Designing luminescent diimine-Cu(i)–phosphine complexes by tuning N-ligand and counteranions: correlation of weak interactions, luminescence and THz absorption spectra
Sun, Zhen-Zhou; Zhu, Ning; Pan, Xun; Hu, Fu-Zhen; Wang, Guo; Yang, Yu-Ping; Qiu, Qi-Ming; Li, Zhong-Feng; Xin, Xiu-Lan; Liu, Jian-Ming; Li, Xiao-Qi; Jin, Qiong-Hua; Ren, Zhi-Gang; Zhou, Qing-Li; CrystEngComm  (2022) –; doi:10.1039/D1CE01574E

data_7244264
_publ_section_title
;
 Designing luminescent diimine-Cu(i)--phosphine complexes by tuning
 N-ligand and counteranions: correlation of weak interactions,
 luminescence and THz absorption spectra
;
_journal_name_full               CrystEngComm
_journal_paper_doi               10.1039/D1CE01574E
_journal_year                    2022
_chemical_formula_moiety         'C45 H40 Cu N4 P2, B F4'
_chemical_formula_sum            'C45 H40 B Cu F4 N4 P2'
_chemical_formula_weight         849.10
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2021-11-23 deposited with the CCDC.	2022-01-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.0520(9)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   24.6200(2)
_cell_length_b                   10.20780(9)
_cell_length_c                   31.7453(3)
_cell_measurement_reflns_used    33035
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      73.6030
_cell_measurement_theta_min      3.6480
_cell_volume                     7899.45(12)
_computing_cell_refinement       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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  29.00   0.50    0.50    --    0.00 -77.00 -60.00  236
  2  \w    -89.00  17.00   0.50    0.50    --    0.00 -37.00 -60.00  212
  3  \w    -89.00  18.00   0.50    0.50    --    0.00 -19.00-180.00  214
  4  \w    -17.00  89.00   0.50    0.50    --    0.00  37.00-150.00  212
  5  \w    -12.00  87.00   0.50    0.50    --    0.00  37.00 150.00  198
  6  \w     25.00 101.00   0.50    1.00    --   94.60 -61.00   0.00  152
  7  \w     21.00 115.00   0.50    1.00    --   94.60 -61.00-150.00  188
  8  \w     22.00 125.00   0.50    1.00    --   94.60 -82.00   0.00  206
  9  \w    104.00 184.00   0.50    1.00    --   94.60  30.00   0.00  160
 10  \w    149.00 177.00   0.50    1.00    --   94.60  30.00-150.00   56
 11  \w     26.00 110.00   0.50    1.00    --   94.60 -61.00  90.00  168
 12  \w    113.00 184.00   0.50    1.00    --   94.60  15.00 -60.00  142
 13  \w      7.00  44.00   0.50    1.00    --   94.60 -82.00  90.00   74
 14  \w      9.00  39.00   0.50    1.00    --   94.60 -82.00 -90.00   60
 15  \w     78.00 104.00   0.50    1.00    --   94.60 -82.00 150.00   52
 16  \w     80.00 184.00   0.50    1.00    --   94.60  30.00 -30.00  208
 17  \w     90.00 119.00   0.50    1.00    --   94.60 -82.00 -90.00   58
 18  \w     62.00 124.00   0.50    1.00    --   94.60 -82.00  90.00  124
 19  \w     11.00  49.00   0.50    1.00    --   94.60 -45.00 -60.00   76
 20  \w     80.00 106.00   0.50    1.00    --   94.60 -45.00 -60.00   52
 21  \w     30.00  56.00   0.50    1.00    --   94.60 -82.00 150.00   52
 22  \w     74.00 100.00   0.50    1.00    --   94.60  15.00 -60.00   52
 23  \w     10.00  49.00   0.50    1.00    --   94.60 -30.00  60.00   78
 24  \w     12.00 124.00   0.50    1.00    --   94.60 -82.00-145.01  224
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0438669000
_diffrn_orient_matrix_UB_12      0.0162767000
_diffrn_orient_matrix_UB_13      0.0297537000
_diffrn_orient_matrix_UB_21      -0.0049385000
_diffrn_orient_matrix_UB_22      -0.1499788000
_diffrn_orient_matrix_UB_23      0.0030646000
_diffrn_orient_matrix_UB_31      0.0452689000
_diffrn_orient_matrix_UB_32      -0.0005645000
_diffrn_orient_matrix_UB_33      0.0388268000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0547
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            41728
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        66.598
_diffrn_reflns_theta_max         66.598
_diffrn_reflns_theta_min         3.626
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.028
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.51565
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.33c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.428
_exptl_crystal_description       block
_exptl_crystal_F_000             3504
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.709
_refine_diff_density_min         -0.801
_refine_diff_density_rms         0.091
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     516
_refine_ls_number_reflns         6957
_refine_ls_number_restraints     948
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0440
_refine_ls_R_factor_gt           0.0432
_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^)+(0.0499P)^2^+24.6325P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1082
_refine_ls_wR_factor_ref         0.1088
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6773
_reflns_number_total             6957
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ce01574e2.cif
_cod_data_source_block           zn-542
_cod_original_cell_volume        7899.46(13)
_cod_database_code               7244264
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Cu1 C1 H1 N1 P1 B1 F1'
_reflns_odcompleteness_completeness 99.51
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33
\\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41
\\sim C42 \\sim C43 \\sim C44 \\sim C45: within 3.8A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 3.8A
3.a Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C33(H33A,H33B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C8(H8), C9(H9), C11(H11), C12(H12), C16(H16), C17(H17),
 C18(H18), C19(H19), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C28(H28),
  C29(H29), C30(H30), C31(H31), C32(H32), C35(H35), C36(H36), C37(H37),
 C38(H38), C39(H39), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45)
3.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C)
;
_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 4.536
_oxdiff_exptl_absorpt_empirical_full_min 0.451