Heteroleptic copper(i) complexes bearing functionalized 1H-pyrazole-bipyridine ligands: synthesis, photophysical properties, crystal structures, and applications in halogen sensing
Tong, Jin; Zhao, Li-Rong; Zhang, Jin; Wang, Xia-Yan; Yu, Yan-Min; Yu, Shu-Yan; New Journal of Chemistry 47 (2023) 4374–4385; doi:10.1039/D2NJ05408F

data_7062331
_publ_section_title
;
 Heteroleptic copper(i) complexes bearing functionalized
 1H-pyrazole-bipyridine ligands: synthesis, photophysical properties,
 crystal structures, and applications in halogen sensing
;
_journal_issue                   9
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              4374
_journal_page_last               4385
_journal_paper_doi               10.1039/D2NJ05408F
_journal_volume                  47
_journal_year                    2023
_chemical_formula_moiety         '2(C49 H38 Cu N4 O P2), 2(C H2 Cl2), 2(B F4)'
_chemical_formula_sum            'C100 H80 B2 Cl4 Cu2 F8 N8 O2 P4'
_chemical_formula_weight         1992.10
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-12-10
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-01-08 deposited with the CCDC.	2023-01-13 downloaded from the CCDC.
;
_cell_angle_alpha                67.431(3)
_cell_angle_beta                 76.762(2)
_cell_angle_gamma                86.734(2)
_cell_formula_units_Z            2
_cell_length_a                   14.1686(3)
_cell_length_b                   17.2839(5)
_cell_length_c                   22.4313(6)
_cell_measurement_reflns_used    14923
_cell_measurement_temperature    293
_cell_measurement_theta_max      73.2600
_cell_measurement_theta_min      3.9450
_cell_volume                     4934.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_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      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3376
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.975
_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    -70.00  32.00   1.00    2.00    --  -41.56  57.00-120.00  102
  2  \w    -96.00  -2.00   1.00    2.00    --  -41.56 125.00-120.00   94
  3  \w   -114.00 -13.00   1.00    2.00    --  -41.56 -57.00  90.00  101
  4  \w   -116.00 -17.00   1.00    2.00    --  -41.56 -38.00 -30.00   99
  5  \w    -11.00  78.00   1.00    2.00    --   41.56 -88.00 -23.00   89
  6  \w     24.00 109.00   1.00    2.00    --  107.13 -94.00 120.00   85
  7  \w     34.00 121.00   1.00    2.00    --  107.13-125.00   0.00   87
  8  \w     94.00 178.00   1.00    2.00    --  107.13 125.00-180.00   84
  9  \w     75.00 178.00   1.00    2.00    --  107.13  77.00 -90.00  103
 10  \w     34.00 121.00   1.00    2.00    --  107.13-125.00  60.00   87
 11  \w     34.00 121.00   1.00    2.00    --  107.13-125.00 -60.00   87
 12  \w     81.00 178.00   1.00    2.00    --  107.13  45.00-180.00   97
 13  \w     81.00 178.00   1.00    2.00    --  107.13  45.00-120.00   97
 14  \w     75.00 178.00   1.00    2.00    --  107.13  77.00 -30.00  103
 15  \w     35.00 136.00   1.00    2.00    --  107.13 -61.00 150.00  101
 16  \w     78.00 178.00   1.00    2.00    --  107.13  61.00 120.00  100
 17  \w    -66.00  33.00   1.00    2.00    --  -41.56  38.00 150.00   99
 18  \w   -118.00  -9.00   1.00    2.00    --  -41.56 -77.00-120.00  109
 19  \w   -118.00 -32.00   1.00    2.00    --  -41.56 -77.00 -30.00   86
 20  \w      9.00 118.00   1.00    2.00    --   41.56  77.00-180.00  109
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0772748000
_diffrn_orient_matrix_UB_12      0.0602387000
_diffrn_orient_matrix_UB_13      -0.0566005000
_diffrn_orient_matrix_UB_21      -0.0784250000
_diffrn_orient_matrix_UB_22      0.0387422000
_diffrn_orient_matrix_UB_23      -0.0393603000
_diffrn_orient_matrix_UB_31      -0.0192209000
_diffrn_orient_matrix_UB_32      0.0647950000
_diffrn_orient_matrix_UB_33      0.0327534000
_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  0.0490
_diffrn_reflns_av_unetI/netI     0.0487
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            56298
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.482
_diffrn_reflns_theta_min         3.453
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.696
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.11192
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.341
_exptl_crystal_description       block
_exptl_crystal_F_000             2040
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         1.040
_refine_diff_density_min         -0.993
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1236
_refine_ls_number_reflns         19665
_refine_ls_number_restraints     45
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0881
_refine_ls_R_factor_gt           0.0672
_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^)+(0.1022P)^2^+4.9500P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1844
_refine_ls_wR_factor_ref         0.2037
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14481
_reflns_number_total             19665
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2nj05408f2.cif
_cod_data_source_block           pzbpy-pop-cubf4
_cod_original_cell_volume        4934.8(2)
_cod_database_code               7062331
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHNOCuBF
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
2. Restrained distances
 F8-B7 \\sim F8A-B7
 with sigma of 0.02
 F7-B7 \\sim F7A-B7
 with sigma of 0.02
 F5-B7 \\sim F5A-B7
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(F1) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(Cl6) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(F5A) \\sim Ueq, Uanis(F8) \\sim Ueq, Uanis(F7A) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(F7) \\sim Ueq, Uanis(F5) \\sim Ueq: with sigma of 0.001 and sigma for
terminal atoms of 0.002
4. Others
 Sof(H52C)=Sof(H52D)=Sof(Cl6)=Sof(Cl5)=Sof(F10)=Sof(F11)=1-FVAR(1)
 Sof(Cl4)=Sof(Cl1)=Sof(F3)=Sof(F1)=Sof(H52A)=Sof(H52B)=FVAR(1)
 Sof(F7A)=Sof(F8A)=Sof(F5A)=1-FVAR(2)
 Sof(F7)=Sof(F5)=Sof(F8)=FVAR(2)
5.a Secondary CH2 refined with riding coordinates:
 C52(H52A,H52B), C52(H52C,H52D), C53(H53A,H53B)
5.b Aromatic/amide H refined with riding coordinates:
 N8(H8A), N3(H3), C98(H98), C61(H61), C102(H102), C10(H10), C88(H88), C36(H36),
  C1(H1), C38(H38), C99(H99), C42(H42), C66(H66), C7(H7), C93(H93), C84(H84),
 C22(H22), C54(H54), C59(H59), C18(H18), C65(H65), C8(H8), C58(H58), C85(H85),
 C63(H63), C64(H64), C77(H77), C71(H71), C13(H13), C81(H81), C55(H55), C86(H86),
  C2(H2), C4(H4), C33(H33), C95(H95), C31(H31), C39(H39), C21(H21), C75(H75),
 C101(H101), C14(H14), C100(H100), C67(H67), C87(H87), C79(H79), C35(H35),
 C45(H45), C3(H3A), C49(H49), C34(H34), C91(H91), C92(H92), C40(H40), C24(H24),
 C80(H80), C41(H41), C78(H78), C15(H15), C20(H20), C96(H96), C28(H28), C26(H26),
  C73(H73), C74(H74), C68(H68), C70(H70), C12(H12), C17(H17), C27(H27),
 C69(H69), C16(H16), C46(H46), C47(H47), C25(H25), C48(H48)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              69293
_shelx_fab_checksum              9343
_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 6.985
_oxdiff_exptl_absorpt_empirical_full_min 0.667