Construction of sterically bent π-conjugated arylene by implanting into bulky NHC Cu(i) coordination polymers in crystalline media
Tomita, Ryunosuke; Jin, Mingoo; CrystEngComm 27 (2025) 5618–5624; doi:10.1039/D5CE00346F

data_7250616
_publ_section_title
;
 Construction of sterically bent \p-conjugated arylene by implanting into
 bulky NHC Cu(i) coordination polymers in crystalline media
;
_journal_issue                   33
_journal_name_full               CrystEngComm
_journal_page_first              5618
_journal_page_last               5624
_journal_paper_doi               10.1039/D5CE00346F
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C39 H44 Cu N4, C32 H12 B F24'
_chemical_formula_sum            'C71 H56 B Cu F24 N4'
_chemical_formula_weight         1495.54
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-15
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2025-03-29 deposited with the CCDC.	2025-07-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.9216(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.27189(4)
_cell_length_b                   15.93292(4)
_cell_length_c                   36.59908(11)
_cell_measurement_reflns_used    196072
_cell_measurement_temperature    153
_cell_measurement_theta_max      76.2050
_cell_measurement_theta_min      2.4330
_cell_volume                     7069.53(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      153
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.971
_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    -92.00 -11.00   0.50    0.32    --  -48.77 121.00  12.00  162
  2  \w    -37.00 -10.00   0.50    0.32    --    6.00 120.00  57.19   54
  3  \w     -7.00  25.00   0.50    0.32    --   22.00  97.00 100.68   64
  4  \w     15.00  40.00   0.50    0.32    --   42.00  90.00  42.27   50
  5  \w     33.00  60.00   0.50    0.32    --   54.00  79.00  16.37   54
  6  \w     63.00  89.00   0.50    0.32    --   54.00  80.00 -10.21   52
  7  \w     81.00 125.00   0.50    0.32    --   54.00  79.00  16.37   88
  8  \w     88.00 127.00   0.50    0.32    --  102.75 121.00  12.00   78
  9  \w     57.00  83.00   0.50    0.32    --   78.00  79.00 -66.43   52
 10  \w     53.00  79.00   0.50    0.32    --   74.00  77.00 -40.81   52
 11  \w     48.00  73.00   0.50    0.32    --   70.00  80.00 -75.61   50
 12  \w     45.00  72.00   0.50    0.32    --   62.00  72.00 -77.53   54
 13  \w     41.00  75.00   0.50    0.32    --   62.00  79.00-130.45   68
 14  \w     45.00  70.00   0.50    0.32    --   66.00  77.00-160.67   50
 15  \w     50.00  76.00   0.50    0.32    --   70.00  75.00-124.68   52
 16  \w     32.00  61.00   0.50    0.32    --   54.00  80.00-125.42   58
 17  \w     32.00  68.00   0.50    0.32    --   54.00  80.00 -67.70   72
 18  \w     45.00  71.00   0.50    0.32    --   66.00  77.00 -48.06   52
 19  \w     46.00  72.00   0.50    0.32    --   66.00  76.00   1.73   52
 20  \w     42.00  69.00   0.50    0.32    --   62.00  76.00  47.79   54
 21  \w     53.00  97.00   0.50    0.32    --   74.00  79.00  44.15   88
 22  \w     41.00  78.00   0.50    0.32    --   62.00  79.00  80.89   74
 23  \w     49.00  75.00   0.50    0.32    --   70.00  77.00 112.84   52
 24  \w     96.00 121.00   0.50    0.32    --   50.00  79.00 176.25   50
 25  \w     98.00 142.00   0.50    0.32    --   70.00  77.00 160.18   88
 26  \w     88.00 113.00   0.50    0.32    --  102.75 152.00 172.00   50
 27  \w     74.00 121.00   0.50    0.32    --   48.77 152.00 172.00   94
 28  \w     41.00  67.00   0.50    0.32    --   62.00  79.00 146.30   52
 29  \w     49.00  75.00   0.50    0.32    --   70.00  77.00 160.18   52
 30  \w     50.00  76.00   0.50    0.32    --   70.00  75.00  97.07   52
 31  \w     32.00 100.00   0.50    0.32    --   54.00  80.00 121.43  136
 32  \w     32.00  62.00   0.50    0.32    --   54.00  80.00 -10.21   60
 33  \w     41.00  67.00   0.50    0.32    --   62.00  78.00  23.95   52
 34  \w     40.00  66.00   0.50    0.32    --   62.00  80.00  67.87   52
 35  \w     28.00  54.00   0.50    0.32    --   50.00  80.00  84.66   52
 36  \w     11.00  36.00   0.50    0.32    --   38.00  92.00 169.65   50
 37  \w     29.00  65.00   0.50    0.32    --   50.00  79.00 176.25   72
 38  \w      0.00  26.00   0.50    0.32    --   30.00  96.00  16.06   52
 39  \w     29.00  56.00   0.50    0.32    --   50.00  79.00 -28.21   54
 40  \w     36.00  75.00   0.50    0.32    --   58.00  80.00-107.54   78
 41  \w     38.00  63.00   0.50    0.32    --   58.00  76.00-163.25   50
 42  \w     26.00  56.00   0.50    0.32    --   46.00  78.00-138.72   60
 43  \w     11.00  36.00   0.50    0.32    --   38.00  90.00 -66.61   50
 44  \w    -16.00  16.00   0.50    0.32    --   14.00  97.00 -14.72   64
 45  \w    -14.00  16.00   0.50    0.32    --   18.00 101.00-142.68   60
 46  \w    -64.00 -30.00   0.50    0.32    -- -102.00  57.00 -60.00   68
 47  \w    -64.00 -30.00   0.50    0.32    -- -102.00  57.00  60.00   68
 48  \w    -69.00 -32.00   0.50    0.32    -- -102.00 109.00 143.50   74
 49  \w    -89.00 -57.00   0.50    0.32    -- -102.00 152.00 172.00   64
 50  \w    -82.00 -37.00   0.50    0.32    -- -102.00 125.00 150.00   90
 51  \w    -93.00 -68.00   0.50    0.32    --  -48.77 152.00 172.00   50
 52  \w    -38.00 -13.00   0.50    0.32    --    6.00 123.00 133.83   50
 53  \w   -109.00 -37.00   0.50    0.32    -- -102.00 121.00  12.00  144
 54  \w   -108.00 -83.00   0.50    0.32    -- -102.00 109.00 143.50   50
 55  \w   -130.00-104.00   0.50    0.32    -- -102.00 152.00 172.00   52
 56  \w   -114.00 -71.00   0.50    0.32    --  -86.00 -66.00-144.86   86
 57  \w    -86.00 -56.00   0.50    0.32    --  -78.00 -79.00-110.06   60
 58  \w    -89.00 -52.00   0.50    0.32    --  -74.00 -79.00 -87.23   74
 59  \w    -94.00 -68.00   0.50    0.32    --  -86.00 -71.00 -87.81   52
 60  \w    -99.00 -66.00   0.50    0.32    --  -86.00 -74.00 -31.69   66
 61  \w    -88.00 -62.00   0.50    0.32    --  -82.00 -74.00  11.63   52
 62  \w    -88.00 -61.00   0.50    0.32    --  -82.00 -78.00  74.98   54
 63  \w    -94.00 -52.00   0.50    0.32    --  -74.00 -79.00 126.90   84
 64  \w    -95.00 -62.00   0.50    0.32    --  -82.00 -74.00 117.96   66
 65  \w    -93.00 -64.00   0.50    0.32    --  -82.00 -71.00 102.73   58
 66  \w    -93.00 -67.00   0.50    0.32    --  -86.00 -73.00 143.25   52
 67  \w    -98.00 -73.00   0.50    0.32    --  -90.00 -67.00 126.67   50
 68  \w    -96.00 -70.00   0.50    0.32    --  -90.00 -76.00  65.13   52
 69  \w    -95.00 -70.00   0.50    0.32    --  -90.00 -74.00   3.53   50
 70  \w   -101.00 -72.00   0.50    0.32    --  -90.00 -72.00 -56.86   58
 71  \w    -95.00 -70.00   0.50    0.32    --  -90.00 -76.00-107.83   50
 72  \w    -99.00 -64.00   0.50    0.32    --  -82.00 -71.00-169.50   70
 73  \w    -95.00 -70.00   0.50    0.32    --  -90.00 -74.00-175.33   50
 74  \w    -99.00 -70.00   0.50    0.32    --  -90.00 -74.00 -98.33   58
 75  \w   -113.00 -66.00   0.50    0.32    --  -86.00 -74.00   6.67   94
 76  \w   -105.00 -73.00   0.50    0.32    --  -94.00 -78.00   7.49   64
 77  \w   -115.00 -66.00   0.50    0.32    --  -86.00 -75.00 -48.17   98
 78  \w   -142.00-102.00   0.50    0.32    --  -90.00 -76.00-107.83   80
 79  \w   -150.00-125.00   0.50    0.32    -- -102.00-121.00 -69.00   50
 80  \w   -153.00-124.00   0.50    0.32    --  -86.00 -75.00 -48.17   58
 81  \w   -160.00-116.00   0.50    0.32    --  -90.00 -72.00 -56.86   88
 82  \w   -160.00 -70.00   0.50    0.32    --  -90.00 -76.00  -9.11  180
 83  \w   -119.00 -81.00   0.50    0.32    --  -48.77-152.00 130.00   76
 84  \w   -134.00-109.00   0.50    0.32    -- -102.00-152.00 130.00   50
 85  \w   -158.00-126.00   0.50    0.32    --  -86.00 -73.00 143.25   64
 86  \w   -111.00 -67.00   0.50    0.32    --  -86.00 -75.00 159.42   88
 87  \w   -106.00 -70.00   0.50    0.32    --  -90.00 -74.00 173.43   72
 88  \w   -103.00 -78.00   0.50    0.32    --  -94.00 -65.00 144.73   50
 89  \w   -127.00 -77.00   0.50    0.32    --  -98.00 -79.00 130.52  100
 90  \w   -158.00-119.00   0.50    0.32    --  -86.00 -75.00 159.42   78
 91  \w   -161.00 -70.00   0.50    0.32    --  -90.00 -75.00  98.80  182
 92  \w   -151.00 -70.00   0.50    0.32    --  -90.00 -74.00  45.57  162
 93  \w   -153.00-112.00   0.50    0.32    --  -90.00 -74.00 173.43   82
 94  \w   -161.00 -70.00   0.50    0.32    --  -90.00 -74.00  83.90  182
 95  \w   -161.00-108.00   0.50    0.32    --  -90.00 -74.00   3.53  106
 96  \w   -158.00 -71.00   0.50    0.32    --  -90.00 -73.00  35.10  174
 97  \w   -158.00 -70.00   0.50    0.32    --  -90.00 -74.00-143.07  176
 98  \w   -161.00-110.00   0.50    0.32    --  -90.00 -74.00-175.33  102
 99  \w   -160.00 -72.00   0.50    0.32    --  -90.00 -71.00 -76.80  176
100  \w   -160.00 -69.00   0.50    0.32    --  -90.00 -77.00-116.33  182
101  \w   -164.00 -73.00   0.50    0.32    --  -94.00 -77.00-147.08  182
102  \w   -165.00-140.00   0.50    0.32    --  -94.00 -78.00   7.49   50
103  \w   -174.00 -83.00   0.50    0.32    -- -102.00 -72.00 -28.43  182
104  \w   -162.00-109.00   0.50    0.32    --  -94.00 -65.00 144.73  106
105  \w   -169.00-132.00   0.50    0.32    --  -98.00 -79.00 130.52   74
106  \w     19.00  88.00   0.50    0.32    --   48.77-121.00 -69.00  138
107  \w     78.00 104.00   0.50    0.32    --  102.75-121.00 -69.00   52
108  \w     49.00  75.00   0.50    0.32    --  102.75-121.00 -69.00   52
109  \w     42.00 106.00   0.50    0.32    --  102.75 -99.00 -60.00  128
110  \w     40.00 105.00   0.50    0.32    --  102.75 -99.00   0.00  130
111  \w     66.00 122.00   0.50    0.32    --  102.75 -77.00  90.00  112
112  \w     71.00 103.00   0.50    0.32    --   48.77-152.00 130.00   64
113  \w     59.00 119.00   0.50    0.32    --  102.75-152.00 130.00  120
114  \w     36.00  85.00   0.50    0.32    --  102.75 -99.00 -30.00   98
115  \w     31.00  69.00   0.50    0.32    --  102.75 -57.00   0.00   76
116  \w     31.00  69.00   0.50    0.32    --  102.75 -57.00  60.00   76
117  \w     32.00 103.00   0.50    0.32    --  102.75 -99.00 120.00  142
118  \w     31.00  69.00   0.50    0.32    --  102.75 -57.00  90.00   76
119  \w     48.00 106.00   0.50    0.32    --  102.75 -99.00-150.00  116
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1235257000
_diffrn_orient_matrix_UB_12      -0.0155588000
_diffrn_orient_matrix_UB_13      0.0135972000
_diffrn_orient_matrix_UB_21      0.0189573000
_diffrn_orient_matrix_UB_22      0.0953053000
_diffrn_orient_matrix_UB_23      0.0043582000
_diffrn_orient_matrix_UB_31      -0.0230397000
_diffrn_orient_matrix_UB_32      -0.0050248000
_diffrn_orient_matrix_UB_33      0.0401370000
_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  0.0415
_diffrn_reflns_av_unetI/netI     0.0101
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            255188
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.317
_diffrn_reflns_theta_min         2.444
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.390
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66601
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.69a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.405
_exptl_crystal_description       block
_exptl_crystal_F_000             3040
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0
_exptl_crystal_size_min          0
_refine_diff_density_max         0.881
_refine_diff_density_min         -0.650
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1006
_refine_ls_number_reflns         14384
_refine_ls_number_restraints     165
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0546
_refine_ls_R_factor_gt           0.0541
_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^)+(0.0716P)^2^+7.0740P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1438
_refine_ls_wR_factor_ref         0.1442
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14153
_reflns_number_total             14384
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00346f2.cif
_cod_data_source_block           NHC-Cu(I)-coordination-polymer-3
_cod_depositor_comments
'Adding full bibliography for 7250614--7250616.cif.'
_cod_original_cell_volume        7069.53(3)
_cod_database_code               7250616
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C H N B F Cu'
_shelx_estimated_absorpt_t_max   1.000
_shelx_estimated_absorpt_t_min   0.873
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C024-F02E \\sim C024-F02F
 with sigma of 0.02
 C024-F02L \\sim C024-F3
 with sigma of 0.02
 C024-F02M \\sim C024-F02N
 with sigma of 0.02
 F00A-C023 \\sim F5-C023
 with sigma of 0.02
 F00C-C023 \\sim F00D-C023
 with sigma of 0.02
 F00L-C023 \\sim F00M-C023
 with sigma of 0.02
 F00F-C02H \\sim F1-C02H
 with sigma of 0.02
 F01L-C02H \\sim F01M-C02H
 with sigma of 0.02
 F02A-C02H \\sim F02B-C02H
 with sigma of 0.02
3. Rigid bond restraints
 F00F, F01L, F02A, C02H, F1, F02B, F01M
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
F00F \\sim F01L \\sim F02A \\sim C02H \\sim F1 \\sim F02B \\sim F01M: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 1.7A
Uanis(F02A) \\sim Ueq, Uanis(F01L) \\sim Ueq, Uanis(F00F) \\sim Ueq: with sigma
of 0.1 and sigma for terminal atoms of 0.2
Uanis(C024) \\sim Ueq, Uanis(F02E) \\sim Ueq, Uanis(F02L) \\sim Ueq,
Uanis(F02M) \\sim Ueq, Uanis(F3) \\sim Ueq, Uanis(F02F) \\sim Ueq, Uanis(F02N)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(F00F) \\sim Ueq, Uanis(F01L) \\sim Ueq, Uanis(F02A) \\sim Ueq,
Uanis(C02H) \\sim Ueq, Uanis(F1) \\sim Ueq, Uanis(F02B) \\sim Ueq, Uanis(F01M)
\\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
5. Rigid body (RIGU) restrains
 F01L, F02A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(F3)=Sof(F02F)=Sof(F02N)=1-FVAR(1)
 Sof(F02E)=Sof(F02L)=Sof(F02M)=FVAR(1)
 Sof(F00M)=Sof(F00D)=Sof(F5)=1-FVAR(2)
 Sof(F00A)=Sof(F00C)=Sof(F00L)=FVAR(2)
 Sof(F1)=Sof(F02B)=Sof(F01M)=1-FVAR(3)
 Sof(F00F)=Sof(F01L)=Sof(F02A)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C01S(H01S), C01T(H01T), C02K(H02K)
7.b Aromatic/amide H refined with riding coordinates:
 C00K(H00K), C00Q(H00Q), C00S(H00S), C00V(H00V), C00X(H00X), C00Z(H00Z),
 C010(H010), C014(H014), C016(H016), C017(H017), C01H(H01H), C01J(H01J),
 C01M(H01M), C01N(H01N), C01O(H01O), C01P(H01P), C01U(H01U), C01V(H01V),
 C01W(H01W), C01X(H01X), C020(H020), C021(H021), C026(H026), C027(H027),
 C028(H028), C029(H029), C02B(H02B), C02F(H02F)
7.c Idealised Me refined as rotating group:
 C02J(H02A,H02C,H02D), C02N(H02E,H02G,H02H), C02O(H02I,H02J,H02L), C02P(H02M,
 H02N,H02O), C02Q(H02P,H02Q,H02R), C02R(H02S,H02T,H02U), C02S(H02V,H02W,H02X),
 C02U(H02Y,H,HA)
;
_shelx_res_checksum              28484
_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 1.399
_oxdiff_exptl_absorpt_empirical_full_min 0.707